Pesticidally active 1,2,4-triazole derivatives with sulphur containing substituents

ABSTRACT

Compounds of formula (I) wherein the substituents are as defined in claim  1 , and the agrochemically acceptable salts salts, stereoisomers, enantiomers, tautomers and N-oxides of those compounds, can be used as insecticides and can be prepared in a manner known per se.

The present invention relates to pesticidally active, in particularinsecticidally active heterocyclic derivatives containing sulphursubstituents, to processes for their preparation, to compositionscomprising those compounds, and to their use for controlling animalpests, including arthropods and in particular insects or representativesof the order Acarina.

Heterocyclic compounds with pesticidal action are known and described,for example, in WO 2010/125985, WO 2013/018928 and EP 1123287. Therehave now been found novel pesticidally active heterocyclic triazolederivatives with sulphur containing phenyl and pyridyl substituents.

The present invention accordingly relates to compounds of formula I,

wherein

G₁ is nitrogen or CR₂;

G₂ is nitrogen or CR₃;

G₃ is nitrogen or CR₄;

G₄ is nitrogen or CR₅;

G₅ is nitrogen or CR₆, with the proviso that not more than 2 nitrogensas G may follow consecutively;

R₂, R₃, R₄, R₅ or R₆ are, independently from each other, hydrogen,halogen, C₁-C₄haloalkyl, C₁-C₄haloalkyl substituted by one or twohydroxy, C₁-C₄haloalkyl substituted by one or two methoxy,C₁-C₄haloalkyl substituted by one or two cyano; or

R₂, R₃, R₄, R₅ or R₆ are, independently from each other,C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl,C₁-C₄haloalkoxy, SF₅, phenylcarbonylthio, cyano, mercapto,C₁-C₄alkoxycarbonyl, C₁-C₄alkylcarbonyl or —C(O)C₁-C₄haloalkyl; or

R₂, R₃, R₄, R₅ or R₆ are, independently from each other, C₃-C₆cycloalkylwhich can be mono- or polysubstituted by substituents selected from thegroup consisting of halogen, cyano and C₁-C₄alkyl;

or two adjacent R_(i), wherein R_(i) is selected from R₂, R₃, R₄, R₅ andR₆, taken together may form a fragment —OCH₂O— or —OCF₂O—;

R₈ is hydrogen, C₁-C₄alkyl or C₁-C₄haloalkyl;

R₇ is a radical selected from the group consisting of formula Q₁ and Q₂

wherein the arrow denotes the point of attachment to the triazole ring;

and wherein A represents CH or N;

Q is phenyl which can be mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano, C₁-C₄alkyl,C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy, C₁-C₄haloalkylsulfanyl,C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl;or

Q is a five- to ten-membered monocyclic or fused bicyclic ring systemlinked via a carbon atom to the ring which contains the group A, saidring system can be aromatic, partially saturated or fully saturated andcontains 1 to 4 hetero atoms selected from the group consisting ofnitrogen, oxygen and sulfur, it not being possible for each ring systemto contain more than 2 oxygen atoms and more than 2 sulfur atoms, saidfive- to ten-membered ring system can be mono- to polysubstituted bysubstituents independently selected from the group consisting ofhalogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl; or

Q is a five- to six-membered, aromatic, partially saturated or fullysaturated ring system linked via a nitrogen atom to the ring whichcontains the group A, said ring system can be mono- or polysubstitutedby substituents selected from the group consisting of halogen, cyano,C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy,C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl; and said ring systemcontains 1, 2 or 3 heteroatoms selected from the group consisting ofnitrogen, oxygen and sulfur, where said ring system may not contain morethan one oxygen atom and not more than one sulfur atom; or

Q is C₃-C₆cycloalkyl, or C₃-C₆cycloalkyl mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano,C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl and phenyl, wherein saidphenyl can be mono- or polysubstituted by substituents selected from thegroup consisting of halogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl,C₁-C₄haloalkoxy, C₁-C₄alkoxy, C₁-C₄haloalkylsulfanyl,C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl;or

Q is C₂-C₆alkenyl, or C₂-C₆alkenyl mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano,C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, C₃-C₆cycloalkyl and phenyl,wherein said phenyl can be mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano, C₁-C₄alkyl,C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy, C₁-C₄haloalkylsulfanyl,C₁-C₄halo-alkylsulfinyl, C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl;or

Q is C₂-C₆alkynyl, or C₂-C₆alkynyl mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano,C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl, tri(C₁-C₄alkyl)silyl andphenyl, wherein said phenyl can be mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano,C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy,C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyland —C(O)C₁-C₄haloalkyl; or

Q is C₁-C₆haloalkylsulfanyl, C₁-C₆haloalkylsulfinyl,C₁-C₆haloalkylsulfonyl, C₁-C₆haloalkoxy, —C(O)C₁-C₄haloalkyl,C₁-C₆alkylsulfanyl, C₁-C₆alkylsulfinyl, or C₁-C₆alkylsulfonyl;

X is S, SO or SO₂; and

R₁ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl; or

R₁ is C₃-C₆cycloalkyl mono- or polysubstituted by substituents selectedfrom the group consisting of halogen, cyano and C₁-C₄alkyl; or

R₁ is C₃-C₆cycloalkyl-C₁-C₄alkyl mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano andC₁-C₄alkyl; or

R₁ is C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl;

and agrochemically acceptable salts, stereoisomers, enantiomers,tautomers and N-oxides of the compounds of formula I.

Compounds of formula I which have at least one basic centre can form,for example, acid addition salts, for example with strong inorganicacids such as mineral acids, for example perchloric acid, sulfuric acid,nitric acid, nitrose acid, a phosphorus acid or a hydrohalic acid, withstrong organic carboxylic acids, such as C₁-C₄alkanecarboxylic acidswhich are unsubstituted or substituted, for example by halogen, forexample acetic acid, such as saturated or unsaturated dicarboxylicacids, for example oxalic acid, malonic acid, succinic acid, maleicacid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids,for example ascorbic acid, lactic acid, malic acid, tartaric acid orcitric acid, or such as benzoic acid, or with organic sulfonic acids,such as C₁-C₄alkane- or arylsulfonic acids which are unsubstituted orsubstituted, for example by halogen, for example methane- orp-toluenesulfonic acid. Compounds of formula I which have at least oneacidic group can form, for example, salts with bases, for examplemineral salts such as alkali metal or alkaline earth metal salts, forexample sodium, potassium or magnesium salts, or salts with ammonia oran organic amine, such as morpholine, piperidine, pyrrolidine, a mono-,di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- ordimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, forexample mono-, di- or triethanolamine.

The alkyl groups occurring in the definitions of the substituents can bestraight-chain or branched and are, for example, methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl,hexyl, nonyl, decyl and their branched isomers. Alkylsulfanyl,alkylsulfinyl, alkylsulfonyl, alkoxy, alkenyl and alkynyl radicals arederived from the alkyl radicals mentioned. The alkenyl and alkynylgroups can be mono- or polyunsaturated.

Halogen is generally fluorine, chlorine, bromine or iodine. This alsoapplies, correspondingly, to halogen in combination with other meanings,such as haloalkyl or halophenyl.

Haloalkyl groups preferably have a chain length of from 1 to 6 carbonatoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl,trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl,2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl,1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl,difluoromethyl, trifluoromethyl and dichlorofluoromethyl.

Alkoxy groups preferably have a preferred chain length of from 1 to 6carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy,i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and also theisomeric pentyloxy and hexyloxy radicals; preferably methoxy and ethoxy.

Alkoxyalkyl groups preferably have a chain length of 1 to 6 carbonatoms.

Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl,ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl orisopropoxyethyl.

Alkylsulfanyl is for example methylsulfanyl, ethylsulfanyl,propylsulfanyl, isopropylsulfanyl, butylsulfanyl, pentylsulfanyl, andhexylsulfanyl.

Alkylsulfinyl is for example methylsulfinyl, ethylsulfinyl,propylsulfinyl, isopropylsulfinyl, a butylsulfinyl, pentylsulfinyl, andhexylsulfinyl.

Alkylsulfonyl is for example methylsulfonyl, ethylsulfonyl,propylsulfonyl, isopropylsulfonyl, butylsulfonyl, pentylsulfonyl, andhexylsulfonyl.

The cycloalkyl groups preferably have from 3 to 6 ring carbon atoms, forexample cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

Haloalkoxy groups preferably have a chain length of from 1 to 4 carbonatoms. Haloalkoxy is, for example, difluoromethoxy, trifluoromethoxy or2,2,2-trifluoroethoxy.

Haloalkylsulfanyl groups preferably have a chain length of from 1 to 4carbon atoms. Haloalkylsulfanyl is, for example, difluoromethylsulfanyl,trifluoromethylsulfanyl or 2,2,2-trifluoroethylsulfanyl. Similarconsiderations apply to the radicals C₁-C₄haloalkylsulfinyl andC₁-C₄haloalkylsulfonyl, which may be, for example,trifluoromethylsulfinyl, trifluoromethylsulfonyl or2,2,2-trifluoroethylsulfonyl.

According to the present invention, when two adjacent R_(i), whereinR_(i) is selected from R₂, R₃, R₄, R₅ and R₆, taken together form afragment —OCH₂O— or —OCF₂O— then an additional five-membered dioxolaneor difluoro-dioxolane ring is formed. For example, compounds of theformula I, wherein G₂ is CR₃, G₃ is CR₄, and in which R₃ and R₄ takentogether form the fragment —OCF₂O—, will have the following structure:

In the context of this invention, examples of a five- to six-membered,aromatic, partially saturated or fully saturated ring system that arelinked via a nitrogen atom to the ring which contains the group A, areselected from pyrazole, pyrrole, pyrrolidine, pyrrolidine-2-one,piperidine, morpholine, imidazole, triazole and pyridine-2-one.

In the context of this invention “mono- to polysubstituted” in thedefinition of the substituents, means typically, depending on thechemical structure of the substituents, monosubstituted to seven-timessubstituted, preferably monosubstituted to five-times substituted, morepreferably mono-, double- or triple-substituted.

Free radicals represents methyl groups.

The compounds of formula I according to the invention also includehydrates which may be formed during the salt formation.

According to the present invention, Q as a five- to ten-memberedmonocyclic or fused bicyclic ring system that is linked via a carbonatom to the ring which contains the group A, said ring system can bearomatic, partially saturated or fully saturated and contains 1 to 4hetero atoms selected from the group consisting of nitrogen, oxygen andsulfur, it not being possible for each ring system to contain more than2 oxygen atoms and more than 2 sulfur atoms,

or Q as a three- to ten-membered, monocyclic or fused bicyclic ringsystem which may be aromatic, partially saturated or fully saturated,

is, depending of the number of ring members, preferably selected fromthe group consisting of the following heterocyclic groups:

pyrrolyl; pyrazolyl; isoxazolyl; furanyl; thienyl; imidazolyl; oxazolyl;thiazolyl; isothiazolyl; triazolyl; oxadiazolyl; thiadiazolyl;tetrazolyl; furyl; pyridyl; pyrimidyl; pyrazinyl; pyridazinyl;triazinyl, pyranyl; quinazolinyl; isoquinolinyl; indolizinyl;isobenzofuranylnaphthyridinyl; quinoxalinyl; cinnolinyl; phthalazinyl;benzothiazolyl; benzoxazolyl; benzotriazolyl; indazolyl; indolyl;(1H-pyrrol-1-yl)-; (1H-pyrrol-2-yl)-; (1H-pyrrol-3-yl)-;(1H-pyrazol-1-yl)-; (1H-pyrazol-3-yl)-; (3H-pyrazol-3-yl)-;(1H-pyrazol-4-yl)-; (3-isoxazolyl)-; (5-isoxazolyl)-; (2-furanyl)-;(3-furanyl)-; (2-thienyl)-; (3-thienyl)-; (1H-imidazol-2-yl)-;(1H-imidazol-4-yl)-; (1H-imidazol-5-yl)-; (2-oxazol-2-yl)-;(oxazol-4-yl)-; (oxazol-5-yl)-; (thiazol-2-yl)-; (thiazol-4-yl)-;(thiazol-5-yl)-; (isothiazol-3-yl)-; (isothiazol-5-yl)-;(1H-1,2,3-triazol-1-yl)-; (1H-1,2,4-triazol-3-yl)-;(4H-1,2,4-triazol-4-yl)-; (1H-1,2,4-triazol-1-yl)-;(1,2,3-oxadiazol-2-yl)-; (1,2,4-oxadiazol-3-yl)-;(1,2,4-oxadiazol-4-yl)-; (1,2,4-oxadiazol-5-yl)-;(1,2,3-thiadiazol-2-yl)-; (1,2,4-thiadiazol-3-yl)-;(1,2,4-thiadiazol-4-yl)-; (1,3,4-thiadiazol-5-yl)-; (1H-tetrazol-1-yl)-;(1H-tetrazol-5-yl)-; (2H-tetrazol-5-yl)-; (2-pyridyl)-; (3-pyridyl)-;(4-pyridyl)-; (2-pyrimidinyl)-; (4-pyrimidinyl)-; (5-pyrimidinyl)-;(2-pyrazinyl)-; (3-pyridazinyl)-; (4-pyridazinyl)-;(1,3,5-triazin-2-yl)-; (1,2,4-triazin-5-yl)-; (1,2,4-triazin-6-yl)-;(1,2,4-triazin-3-yl)-; (furazan-3-yl)-; (2-quinolinyl)-;(3-quinolinyl)-; (4-quinolinyl)-; (5-quinolinyl)-; (6-quinolinyl)-;(3-isoquinolnyl)-; (4-isoquinolnyl)-; (2-quinozolinyl)-;(2-quinoxalinyl)-; (5-quinoxalinyl)-; (pyrido[2,3-b]pyrazin-7-yl)-;(benzoxazol-5-yl)-; (benzothiazol-5-yl)-; (benzo[b]thien-2-yl) and(benzo[1,2,5]oxadiazol-5-yl)-; indolinyl and tetrahydroquinolynyl.

In preferred compounds of formula I, Q is selected from the groupconsisting of J-0 to J-51 (where the arrow represents the point ofattachment of the group J to the ring which contains the group A):

in particular selected from J-1 to J-48;

wherein each group J-0 to J-48 is mono-, di- or trisubstituted with Rx,wherein each Rx is, independently selected from hydrogen, halogen,cyano, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy,C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl.

A preferred group of compounds of formula I is represented by thecompounds of formula I-1

wherein A, Q, G₁, G₂, G₃, G₄, and G₅ are as defined under formula Iabove; and wherein X₁ is S, SO or SO₂; and R₁₁ is methyl, ethyl,n-propyl, i-propyl or cyclopropylmethyl; R₈ is as defined above underformula I, preferably methyl, and agrochemically acceptable salts,stereoisomers, enantiomers, tautomers and N-oxides of those compounds.

Embodiment (I-1-A): Also preferred are compounds of formula I-1 with G₁defined as N, G₄ defined as C(C₁-C₄haloalkyl), and G₂, G₃ and G₅ definedas CH.

In an especially preferred group of compounds of formula I-1, G₁ isdefined as N, G₄ is defined as C(CF₃), and G₂, G₃ and G₅ are defined asCH.

Embodiment (I-1-B): Also preferred are compounds of formula I-1 with G₁and G₃ defined as N, G₄ defined as C(C₁-C₄haloalkyl), and G₂ and G₅defined as CH.

In an especially preferred group of compounds of formula I-1, G₁ and G₃are defined as N, G₄ is defined as C(CF₃), and G₂ and G₅ are defined asCH.

In said especially preferred groups of compounds of formula I-1, R₈ ispreferably methyl. A further preferred embodiment of said especiallypreferred groups of compounds of formula I-1 comprises compounds whereinA is preferably N, X₁ is preferably S or SO₂ and R₁₁ is preferablyethyl.

In compounds of formula I-1 and all of the preferred embodiments ofcompounds of formula I-1 mentioned above, Q is preferably selected fromthe group consisting of

in particular selected from J-0, J-1, J-5, J-30, J-35, J-43, J-46 andJ-48;

wherein each group J-0 to J-48 is mono-, di- or trisubstituted with Rx,wherein

each Rx is, independently selected from hydrogen, halogen, cyano,C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy,C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl. Preferably each Rx is,independently selected from hydrogen, halogen, cyano, C₁-C₄haloalkyl andC₁-C₄alkoxy, preferably selected from hydrogen, fluorine, chlorine,cyano, trifluoromethyl and ethoxy;

in particular preferably selected from hydrogen, chlorine, cyano,trifluoromethyl and ethoxy; and

wherein each C₁-C₆haloalkyl group in J-49 to J-51 is preferablytrifluoromethyl.

Another preferred group of compounds of formula I is represented by thecompounds of formula I-2

wherein A, G₁, G₂, G₃, G₄, and G₅ are as defined under formula I above;and wherein X₂ is S, SO or SO₂; and R₁₂ is methyl, ethyl, n-propyl,i-propyl or cyclopropylmethyl; R₈ is as defined above under formula I,preferably methyl, and wherein Qa₁ is selected from the group consistingof

in particular selected from J-0, J-1, J-5, J-30, J-35, J-43, J-46 andJ-48;

wherein each group J-0 to J-48 is mono-, di- or trisubstituted with Rx,wherein

each Rx is, independently selected from hydrogen, halogen, cyano,C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy,C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl, and agrochemicallyacceptable salts, stereoisomers, enantiomers, tautomers and N-oxides ofthose compounds.

Also preferred are compounds of formula I-2, wherein each Rx is,independently selected from hydrogen, halogen, cyano, C₁-C₄haloalkyl andC₁-C₄alkoxy.

More preferred compounds of formula I-2 are those, in which each Rx is,independently from each other, selected from hydrogen, fluorine,chlorine, cyano, trifluoromethyl and ethoxy; in particular selected fromhydrogen, chlorine, cyano, trifluoromethyl and ethoxy.

A further preferred embodiment of the invention comprises compounds offormula I-2 wherein each C₁-C₆haloalkyl group in J-49 to J-51 ispreferably trifluoromethyl.

In an especially preferred group of compounds of formula I-2, Qa₁ isselected from the group consisting of

in particular selected from J-0a, J-1a, J-1b, J-1c, J-5a, J-5b, J-30a,J-30b, J-35a, J-43a, J-46a and J-48a;

wherein each Rx is, independently selected from hydrogen, halogen,cyano, C₁-C₄haloalkyl and C₁-C₄alkoxy, preferably from hydrogen,fluorine, chlorine, cyano, trifluoromethyl and ethoxy; in particularpreferably selected from hydrogen, chlorine, cyano, trifluoromethyl andethoxy; and

wherein each C₁-C₆haloalkyl group in J-49 to J-51 is preferablytrifluoromethyl.

In said especially preferred group of compounds of formula I-2, R₈ ispreferably methyl. A further preferred embodiment of said especiallypreferred group of compounds of formula I-2 comprises compounds whereinA is preferably N, X₂ is preferably S or SO₂ and R₁₂ is preferablyethyl.

A further preferred embodiment of the invention comprises compounds offormula I represented by the compounds of formula I-3

wherein

A is N or CH;

R₁₀ is pyridyl mono- or polysubstituted by substituents independentlyselected from the group consisting of C₁-C₄haloalkyl, in particulartrifluoromethyl; or

R₁₀ is pyrimidyl mono- or polysubstituted by substituents independentlyselected from the group consisting of C₁-C₄haloalkyl, in particulartrifluoromethyl;

X₃ is S, SO or SO₂, in particular S or SO₂;

Qa₂ is selected from the group consisting of

in particular selected from J-0, J-1, J-5, J-30, J-35, J-43, J-46 andJ-48;

wherein each group J-0 to J-48 is mono-, di- or trisubstituted with Rx,wherein each Rx is, independently selected from hydrogen, halogen,cyano, C₁-C₄haloalkyl and C₁-C₄alkoxy;

R₁₃ is C₁-C₄alkyl, in particular methyl or ethyl;

R₈ is C₁-C₄alkyl, in particular methyl or ethyl;

and agrochemically acceptable salts, stereoisomers, enantiomers,tautomers and N-oxides of the compounds of formula I-3.

In said preferred embodiment comprising compounds of formula I-3, R₁₀ ispreferably pyridyl or pyrimidyl, in particular preferably pyridyl,monosubstituted by substituents independently selected from the groupconsisting of C₁-C₄haloalkyl.

Especially preferred substituents on the ring R₁₀ are selected fromtrifluoromethyl.

In said preferred embodiment comprising compounds of formula I-3, Qa₂ ispreferably selected from the group consisting of

in particular selected from J-0a, J-1a, J-1b, J-1c, J-5a, J-5b, J-30a,J-30b, J-35a, J-43a, J-46a and J-48a;

wherein each Rx is, independently selected from hydrogen, halogen,cyano, C₁-C₄haloalkyl and C₁-C₄alkoxy, preferably from hydrogen,fluorine, chlorine, cyano, trifluoromethyl and ethoxy; in particularselected from hydrogen, chlorine, cyano, trifluoromethyl and ethoxy; and

wherein each C₁-C₆haloalkyl group in J-49 to J-51 is preferablytrifluoromethyl.

An especially preferred embodiment of the invention comprises compoundsof formula I represented by the compounds of formula I-4

wherein

R₁₀′ is pyridyl monosubstituted by C₁-C₄haloalkyl; or

R₁₀′ is pyrimidyl monosubstituted by C₁-C₄haloalkyl;

preferably R₁₀′ is pyridyl monosubstituted by C₁-C₄haloalkyl;

and

Qa₄ is selected from the group consisting of

in particular selected from J-0a, J-1a, J-1b, J-1c, J-5a, J-5b, J-30a,J-30b, J-35a, J-43a, J-46a and J-48a;

wherein each Rx is, independently selected from hydrogen, halogen,cyano, C₁-C₄haloalkyl and C₁-C₄alkoxy;

and agrochemically acceptable salts, stereoisomers, enantiomers,tautomers and N-oxides of the compounds of formula I-4.

An even further especially preferred embodiment of the inventioncomprises compounds of formula I represented by the compounds of formulaI-5

wherein

R₅ is independently selected from the group consisting ofC₁-C₄haloalkyl; and

Qa₅ is selected from the group consisting of

in particular selected from J-0a, J-1a, J-1b, J-1c, J-5a, J-5b, J-30a,J-30b, J-35a, J-43a, J-46a and J-48a;

wherein each Rx is, independently selected from hydrogen, halogen,cyano, C₁-C₄haloalkyl and C₁-C₄alkoxy;

and agrochemically acceptable salts, stereoisomers, enantiomers,tautomers and N-oxides of the compounds of formula I-5.

Another even further especially preferred embodiment of the inventioncomprises compounds of formula I represented by the compounds of formulaI-6

wherein

R₆ is independently selected from the group consisting ofC₁-C₄haloalkyl; and

Qa₆ is selected from the group consisting of

wherein each Rx is, independently selected from hydrogen, halogen andcyano;

and agrochemically acceptable salts, stereoisomers, enantiomers,tautomers and N-oxides of the compounds of formula I-6.

Another preferred group of compounds of formula I is represented by thecompounds of formula I-1p

wherein A, Q, G₁, G₂, G₃, G₄, and G₅ are as defined under formula Iabove; preferably Q is as defined for Qa₅ in formula I-5 above; andwherein X₁ is S, SO or SO₂; and R₁₁ is methyl, ethyl, n-propyl, propylor cyclopropylmethyl; R₈ is as defined above under formula I, preferablymethyl, and agrochemically acceptable salts, stereoisomers, enantiomers,tautomers and N-oxides of those compounds.

Embodiment (I-1p-A): Also preferred are compounds of formula I-1p withG₁ defined as N, G₄ defined as C(C₁-C₄haloalkyl), and G₂, G₃ and G₅defined as CH.

In an especially preferred group of compounds of formula I-1p, G₁ isdefined as N, G₄ is defined as C(CF₃), and G₂, G₃ and G₅ are defined asCH.

Embodiment (I-1p-B): Also preferred are compounds of formula I-1p withG₁ and G₃ defined as N, G₄ defined as C(C₁-C₄haloalkyl), and G₂ and G₅defined as CH.

In an especially preferred group of compounds of formula I-1p, G₁ and G₃are defined as N, G₄ is defined as C(CF₃), and G₂ and G₅ are defined asCH.

In said especially preferred groups of compounds of formula I-1p, R₈ ispreferably methyl. A further preferred embodiment of said especiallypreferred groups of compounds of formula I-1p comprises compoundswherein A is preferably N, X₁ is preferably S or SO₂ and R₁₁ ispreferably ethyl.

In compounds of formula I-1p and all of the preferred embodiments ofcompounds of formula I-1p mentioned above, Q is preferably selected fromthe group consisting of

in particular selected from J-0;

wherein each group J-0 to J-43 is mono-, di- or trisubstituted with Rx,wherein

each Rx is, independently selected from hydrogen, halogen, cyano,C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy,C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl.

Preferably each Rx is, independently selected from hydrogen, halogen,cyano and C₁-C₄haloalkyl, in particular selected from hydrogen andC₁-C₄haloalkyl; more preferably each Rx is, independently selected fromhydrogen, fluorine, chlorine, cyano and trifluoromethyl, in particularselected from hydrogen and trifluoromethyl.

Another preferred group of compounds of formula I is represented by thecompounds of formula I-2p

wherein A, Q, G₁, G₂, G₃, G₄, and G₅ are as defined under formula Iabove; preferably Q is as defined for Qa₅ in formula I-5 above; andwherein X₂ is S, SO or SO₂; and R₁₂ is methyl, ethyl, n-propyl, propylor cyclopropylmethyl; R₈ is as defined above under formula I, preferablymethyl, and wherein Q is selected from the group consisting of

in particular selected from J-0;

wherein each group J-0 to J-43 is mono-, di- or trisubstituted with Rx,wherein

each Rx is, independently selected from hydrogen, halogen, cyano,C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy,C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl, and agrochemicallyacceptable salts, stereoisomers, enantiomers, tautomers and N-oxides ofthose compounds.

Also preferred are compounds of formula I-2p, wherein each Rx is,independently selected from hydrogen, halogen, cyano and C₁-C₄haloalkyl,in particular selected from hydrogen and C₁-C₄haloalkyl.

More preferred compounds of formula I-2p are those, in which each Rx is,independently from each other, selected from hydrogen, fluorine,chlorine, cyano and trifluoromethyl, in particular selected fromhydrogen and trifluoromethyl.

In an especially preferred group of compounds of formula I-2p, Q isselected from the group consisting of

in particular selected from J-0a;

wherein each Rx is, independently selected from hydrogen, halogen, cyanoand C₁-C₄haloalkyl, in particular selected from hydrogen andC₁-C₄haloalkyl; more preferably each Rx is, independently selected fromhydrogen, fluorine, chlorine, cyano and trifluoromethyl, in particularselected from hydrogen and trifluoromethyl.

In said especially preferred group of compounds of formula I-2p, R₈ ispreferably methyl. A further preferred embodiment of said especiallypreferred group of compounds of formula I-2p comprises compounds whereinA is preferably N, X₂ is preferably S or SO₂ and R₁₂ is preferablyethyl.

A further preferred embodiment of the invention comprises compounds offormula I represented by the compounds of formula I-3p

wherein

A is N or CH;

R₁₀ is pyridyl or pyrimidyl mono- or polysubstituted by substituentsindependently selected from the group consisting of C₁-C₄haloalkyl, inparticular trifluoromethyl;

X₃ is S, SO or SO₂, in particular S or SO₂;

Qa₂ is selected from the group consisting of

wherein each group J-0 to J-43 is mono-, di- or trisubstituted with Rx,wherein each Rx is, independently selected from hydrogen, halogen, cyanoand C₁-C₄haloalkyl;

R₁₃ is C₁-C₄alkyl, in particular methyl or ethyl;

R₈ is C₁-C₄alkyl, in particular methyl or ethyl;

and agrochemically acceptable salts, stereoisomers, enantiomers,tautomers and N-oxides of the compounds of formula I-3p.

In said preferred embodiment comprising compounds of formula I-3p, R₁₀is preferably pyridyl or pyrimidyl monosubstituted by substituentsindependently selected from the group consisting of C₁-C₄haloalkyl.

Especially preferred substituents on the ring R₁₀ are selected fromtrifluoromethyl.

In said preferred embodiment comprising compounds of formula I-3p, Qa₂is preferably selected from the group consisting of

wherein each Rx is, independently selected from hydrogen, halogen, cyanoand C₁-C₄haloalkyl, preferably from hydrogen, fluorine, chlorine, cyanoand trifluoromethyl.

An especially preferred embodiment of the invention comprises compoundsof formula I represented by the compounds of formula I-4p

wherein

R₁₀′ is pyridyl or pyrimidyl monosubstituted by substituentsindependently selected from the group consisting of C₁-C₄haloalkyl; and

Qa₄ is selected from the group consisting of

wherein each Rx is, independently selected from hydrogen, halogen, cyanoand C₁-C₄haloalkyl;

and agrochemically acceptable salts, stereoisomers, enantiomers,tautomers and N-oxides of the compounds of formula I-4p.

An even further especially preferred embodiment of the inventioncomprises compounds of formula I represented by the compounds of formulaI-5p

wherein

R₅ is independently selected from the group consisting ofC₁-C₄haloalkyl; and

Qa₅ is selected from the group consisting of

wherein each Rx is, independently selected from hydrogen, halogen, cyanoand C₁-C₄haloalkyl;

and agrochemically acceptable salts, stereoisomers, enantiomers,tautomers and N-oxides of the compounds of formula I-5p.

Another even further especially preferred embodiment of the inventioncomprises compounds of formula I represented by the compounds of formulaI-6p

wherein

R₆ is independently selected from the group consisting ofC₁-C₄haloalkyl; and

Qa₆ is selected from the group consisting of

wherein each Rx is, independently selected from hydrogen, halogen, cyanoand C₁-C₄haloalkyl;

and agrochemically acceptable salts, stereoisomers, enantiomers,tautomers and N-oxides of the compounds of formula I-6p.

The process according to the invention for preparing compounds offormula I is carried out in principle by methods known to those skilledin the art. More specifically, the subgroup of compounds of formula I,wherein X is SO (sulfoxide) and/or SO₂ (sulfone), may be obtained bymeans of an oxidation reaction of the corresponding sulfide compounds offormula I, wherein X is S, involving reagents such as, for example,m-chloroperoxybenzoic acid (mCPBA), hydrogen peroxide, oxone, sodiumperiodate, sodium hypochlorite or tert-butyl hypochlorite amongst otheroxidants. The oxidation reaction is generally conducted in the presenceof a solvent. Examples of the solvent to be used in the reaction includealiphatic halogenated hydrocarbons such as dichloromethane andchloroform; alcohols such as methanol and ethanol; acetic acid; water;and mixtures thereof. The amount of the oxidant to be used in thereaction is generally 1 to 3 moles, preferably 1 to 1.2 moles, relativeto 1 mole of the sulfide compounds I to produce the sulfoxide compoundsI, and preferably 2 to 2.2 moles of oxidant, relative to 1 mole of thesulfide compounds I to produce the sulfone compounds I. Such oxidationreactions are disclosed, for example, in WO 2013/018928.

The subgroup of compounds of formula I, wherein X is S (sulfide) andwherein R₇, R₈, G₁, G₂, G₃, G₄, and G₅ are as defined above,

may be prepared by reacting an amidine compound of formula IIa, or asalt thereof (such as a hydrohalide salt, preferably a hydrochloride ora hydrobromide salt, or any other equivalent salt), wherein R₈, G₁, G₂,G₃, G₄, and G₅ are as defined above, with a hydrazide compound offormula III, or a salt thereof, wherein R₇ is as defined above andwherein X is S (sulfide), optionally in presence of a base such asalkali metal carbonates, for example sodium carbonate or potassiumcarbonate, in a solvent such as methanol, ethanol, isopropanol,acetonitrile, pyridine, acetic acid, N,N-dimethyl-formamide orN,N-dimethylacetamide, at temperatures between 0 and 200° C., preferablybetween 50 and 150° C., optionally under microwave irradiation. Such aprocess may be carried out in analogy to, for example, G. Bonanomi etal., ChemMedChem 2010, 5, 705-715. The compounds of formula IIa may bereacted with any configuration (E or Z, or any mixture thereof) on thecarbon-nitrogen double bond.

Alternatively, the subgroup of compounds of formula I, wherein X is S(sulfide) and wherein R₇, R₈, G₁, G₂, G₃, G₄, and G₅ are as definedabove,

may be prepared by reacting an alkyl carboximidothioate compound offormula IIb, or a salt thereof (such as a hydrohalide salt, preferably ahydrochloride or a hydrobromide salt, or any other equivalent salt),wherein R₈, G₁, G₂, G₃, G₄, and G₅ are as defined above, and in which R₉is C₁₋₆alkyl, with a hydrazide compound of formula III, or a saltthereof, wherein R₇ is as defined above and wherein X is S (sulfide),optionally in presence of a base such as alkali metal carbonates, forexample sodium carbonate or potassium carbonate, in a solvent such asmethanol, ethanol, isopropanol, acetonitrile, pyridine, acetic acid,N,N-dimethylformamide or N,N-dimethyl-acetamide, at temperatures between0 and 200° C., preferably between 50 and 180° C., optionally undermicrowave irradiation. Such a process may be carried out in analogy to,for example, M. H. Klingele et al, Eur. J. Org. Chem. 2004, 3422-3434.The compounds of formula IIb may be reacted with any configuration (E orZ, or any mixture thereof) on the carbon-nitrogen double bond.

Compounds of formula IIa, or a salt thereof (such as a hydrohalide salt,preferably a hydrochloride or a hydrobromide salt, or any otherequivalent salt), wherein R₈, G₁, G₂, G₃, G₄, and G₅ are as definedabove,

may be prepared by reacting a nitrile compound of formula IV, whereinG₁, G₂, G₃, G₄, and G₅ are as defined above,

sequentially with

i) a catalytic amount (preferably 0.01 to 0.5 equivalent) or anequimolar amount of an alkoxide, preferably sodium methoxide NaOMe orsodium ethoxide NaOEt, in an alcoholic solvent, such as methanol orethanol, at temperatures between 0 and 100° C., to generate an imidateintermediate of the formula INT₁ (or a salt and/or a tautomer thereof);followed by

ii) treatment with an amine reagent of formula V

R₈—NH₂  (V),

or a salt thereof (such as a hydrohalide salt, preferably ahydrochloride or a hydrobromide salt, or any other equivalent salt),wherein R₈ is as defined above, optionally in the presence of an acid(such as a hydrohalide acid, preferably hydrochloric acid or hydrobromicacid, or any other equivalent acid), at temperatures between 0-180° C.,to generate an amidine intermediate of the formula INT₂ (or a saltand/or a tautomer thereof); followed by

iii) treatment with an excess of the amine reagent of formula V, or asalt thereof (such as a hydrohalide salt, preferably a hydrochloride ora hydrobromide salt, or any other equivalent salt), wherein R₈ is asdefined above, preferably in the presence of an acid (such as ahydrohalide acid, preferably hydrochloric acid or hydrobromic acid, orany other equivalent acid), at temperatures between 0-180° C., to formthe compound of the formula IIa, or a salt and/or a tautomer thereof.The compounds of formula IIa may be isolated with any configuration (Eor Z, or any mixture thereof) on the carbon-nitrogen double bond. Stepsii) and iii) may be combined, for example to allow a direct formation ofa compound of formula IIa from a compound of formula INT₁. Steps ii)and/or iii) may also be performed under microwave irradiation, eachoptionally also in a pressurized vessel. Compounds of the formula INT₁may alternatively be prepared under conditions and variants of thePinner reaction known to a person skilled in the art, typically bytreating a compound of the formula IV with a hydrohalide acid,preferably hydrochloric acid, in presence of alcoholic reagents such asmethanol or ethanol, preferably in an inert solvent such as diethylether, tetrahydrofuran or dioxane, at temperatures between −40 and 50°C., preferably between −20 and 20° C. The described process to preparecompounds of the formula IIa from compounds of the formula IV mayinclude isolation and purification of the intermediates INT₁ and/or INT₂(which may be isolated as free bases or as salts (e.g. a hydrohalidesalt, more specifically a hydrochloride or hydrobromide salt, or anyother equivalent salt)), however this process is advantageouslyconducted as a one-pot preparation. In the particular situation where R₈is methyl or ethyl, the amine reagent of formula V may be engaged in theabove reaction as a gas, as a salt (such as a hydrohalide salt,preferably a hydrochloride or a hydrobromide salt, or any otherequivalent salt), or as a solution in solvents such as methanol,ethanol, tetrahydrofuran or water.

Compounds of formula IIb, or a salt thereof (such as a hydrohalide salt,preferably a hydrochloride or a hydrobromide salt, or any otherequivalent salt), wherein R₈, G₁, G₂, G₃, G₄, and G₅ are as definedabove, and in which R₉ is C₁₋₆alkyl,

may be prepared by reacting a compound of formula INT₄, wherein R₈, G₁,G₂, G₃, G₄, and G₅ are as defined above, with an alkylation reagent offormula V-a, wherein R₉ is C₁₋₆alkyl, and in which X_(LG) is a leavinggroup, such as a halogen (especially bromine or iodine), or a leavinggroup OSO₂R₃₈, wherein R₃₈ is C₁-C₆alkyl, C₁-C₆haloalkyl, or phenyloptionally substituted by nitro or C₁-C₃alkyl (especially a sulfonatesuch as mesylate, triflate or tosylate) or a sulfate (forming forexample the alkylating agent V-a dimethylsulfate, in the particularsituation where R₉ is methyl), preferably in the presence of a suitablebase, such as sodium hydride or sodium, potassium or cesium carbonate,in an inert solvent such as tetrahydrofuran, dioxane, acetonitrile,N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone ordimethyl sulfoxide. Another advantageous base/solvent combination forthis transformation is also, for example, an alkoxide, preferably sodiummethoxide NaOMe or sodium ethoxide NaOEt, in an alcoholic solvent, suchas methanol or ethanol, at temperatures between 0-100° C., preferablyaround room temperature. The compounds of formula IIb may be isolatedwith any configuration (E or Z, or any mixture thereof) on thecarbon-nitrogen double bond. Such a process may be carried out inanalogy to, for example, M. H. Klingele et al, Eur. J. Org. Chem. 2004,3422-3434.

Compounds of formula INT₄, wherein R₈, G₁, G₂, G₃, G₄, and G₅ are asdefined above, may be prepared by reacting a compound of formula INT₃,wherein R₈, G₁, G₂, G₃, G₄, and G₅ are as defined above, with athionation agent, such as phosphorus decasulfide P₄S₁₀ (also calledphosphorus pentasulfide P₂S₅), or the Lawesson reagent(2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-dithione), ininert solvents such as toluene, xylene, tetrahydrofuran, dioxane orpyridine, at temperatures between 0-200° C., preferably between 50 and150° C., optionally under microwave irradiation. Such a process may becarried out in analogy to, for example, T. Ozturk et al., Chem. Rev.2010, 110, 3419-3478.

Compounds of formula INT₃, wherein R₈, G₁, G₂, G₃, G₄, and G₅ are asdefined above, may be prepared by

i) activation of a compound of formula IV-a, wherein G₁, G₂, G₃, G₄, andG₅ are as defined above, by methods known to those skilled in the artand described in, for example, Tetrahedron, 2005, 61 (46), 10827-10852,to form an activated species IV-aa, wherein G₁, G₂, G₃, G₄, and G₅ areas defined above and wherein X₀₀ is halogen, preferably chlorine. Forexample, compounds IV-aa where X₀₀ is halogen, preferably chlorine, areformed by treatment of IV-a with, for example, oxallyl chloride (COCl)₂or thionyl chloride SOCl₂ in the presence of catalytic quantities ofN,N-dimethylformamide DMF in inert solvents such as methylene chlorideCH₂Cl₂ or tetrahydrofuran THF at temperatures between 20 to 100° C.,preferably 25° C. Alternatively, treatment of compounds of formula IV-awith, for example, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide EDC ordicyclohexyl carbodiimide DCC will generate an activated species IV-aa,wherein X₀₀ is X₀₁ or X₀₂ respectively, in an inert solvent, such aspyridine or tetrahydrofuran THF, optionally in the presence of a base,such as triethylamine, at temperatures between 50-180° C.; followed by

ii) treatment of the activated species IV-aa with an amine reagent offormula V

R₈—NH₂  (V),

or a salt thereof (such as a hydrohalide salt, preferably ahydrochloride or a hydrobromide salt, or any other equivalent salt),wherein R₈ is as defined above, optionally in the presence of a base,such as triethylamine or pyridine, in an inert solvents such asdichloromethane, tetrahydrofuran, dioxane or toluene, at temperaturesbetween 0 and 50° C., to form the compounds of formula INT₃. Certainbases, such as pyridine and triethylamine, may be employed successfullyas both base and solvent.

Compounds of formula IV and compounds of formula IV-a, wherein G₁, G₂,G₃, G₄, and G₅ are as defined above, are known compounds or can beprepared by known methods, described in the literature.

Compounds of the formula III, or a salt thereof, wherein R₇ is asdefined above,

may be prepared by

i) activation of compound of formula VI, wherein R₇ is as defined above,by methods known to those skilled in the art and described in, forexample, Tetrahedron, 2005, 61 (46), 10827-10852, to form an activatedspecies VIa, wherein R₇ is as defined above and wherein X₀₀ is halogen,preferably chlorine. For example, compounds VIa where X₀₀ is halogen,preferably chlorine, are formed by treatment of VI with, for example,oxallyl chloride (COCl)₂ or thionyl chloride SOCl₂ in the presence ofcatalytic quantities of N,N-dimethylformamide DMF in inert solvents suchas methylene chloride CH₂Cl₂ or tetrahydrofuran THF at temperaturesbetween 20 to 100° C., preferably 25° C. Alternatively, treatment ofcompounds of formula VI with, for example,1-ethyl-3-(3-dimethylaminopropyl)carbodiimide EDC or dicyclohexylcarbodiimide DCC will generate an activated species VIa, wherein X₀₀ isX₀₁ or X₀₂ respectively, in an inert solvent, such as pyridine ortetrahydrofuran THF, optionally in the presence of a base, such astriethylamine, at temperatures between 50-180° C.; followed by

ii) Treatment of the activated species VIa with hydrazine NH₂NH₂ (or asalt thereof), possibly in form of a hydrate, preferably hydrazinemonohydrate, optionally in the presence of a base, such as triethylamineor pyridine, in an inert solvents such as dichloromethane,tetrahydrofuran, dioxane or toluene, at temperatures between 0 and 50°C., to form the compounds of formula III.

Alternatively, compounds of the formula III, or a salt thereof, whereinR₇ is as defined above, may be prepared by the direct action ofhydrazine (or a salt thereof), possibly in form of a hydrate, preferablyhydrazine monohydrate, on an ester derivative VIb

of the compound of formula VI, wherein R₇ is as defined above andwherein R₀₀ is C₁-C₄alkyl, preferably methyl or ethyl, at temperaturesbetween 20 and 150° C. This reaction is preferably performed in analcoholic solvent, such as methanol or ethanol. Such a processdescription may be found, for example, in M. H. Klingele et al, Eur. J.Org. Chem. 2004, 3422-3434.

Compounds of formula VI and VIb, wherein R₇ is as defined above, areknown compounds or can be prepared by known methods (see in particular,preparation of useful building blocks of formula XIX described below),described in the literature. In particular, ester compounds of formulaVIb, wherein R₇ is as defined above and wherein R₀₀ is C₁-C₄alkyl, maybe prepared from the corresponding carboxylic acid compounds of formulaVI, wherein R₇ is as defined above, by reaction with an alcohol offormula R₀₀OH (XII), wherein R₀₀ is C₁-C₄alkyl, optionally in thepresence of an acid (such as sulfuric acid), or alternatively optionallyin presence of an activating agent, such as for example oxalyl chloride(COCl)₂. Such esterification methods are well known to a person skilledin the art.

Compounds of formula I, wherein R₇, R₈, G₁, G₂, G₃, G₄, and G₅ are asdefined in formula I and wherein X is S (sulfide),

can also be prepared by reacting a compound of formula VII, wherein R₈,G₁, G₂, G₃, G₄, and G₅ are as described in formula I and wherein Q_(a)is a radical selected from the group consisting of formula Q_(1a) toQ_(2a):

wherein A is as defined in formula I, and wherein X₁₀ is a halogen(preferably fluorine, chlorine or bromine), with a compound of formulaVIII

R₁—SH  (VIII),

or a salt thereof, wherein R₁ is as defined in formula I, optionally inthe presence of a suitable base, such as alkali metal carbonates, forexample sodium carbonate and potassium carbonate, or alkali metalhydrides such as sodium hydride, or alkali metal hydroxides such assodium hydroxide and potassium hydroxide, in an inert solvent attemperatures preferably between 25-120° C. Examples of solvent to beused include ethers such as THF, ethylene glycol dimethyl ether,tert-butylmethyl ether, and 1,4-dioxane, aromatic hydrocarbons such astoluene and xylene, nitriles such as acetonitrile or polar aproticsolvents such as N,N-dimethylformamide, N,N-dimethylacetamide,N-methyl-2-pyrrolidone or dimethyl sulfoxide. Examples of salts of thecompound of formula VIII include compounds of the formula VIIIa

R₁—S-M  (VIIIa),

wherein R₁ is as defined above and wherein M is, for example, sodium orpotassium.

Compounds of formula VII, wherein R₈, G₁, G₂, G₃, G₄, and G₅ are asdefined above, and wherein Q_(a) is a radical selected from the groupconsisting of formula Q_(1a) to Q_(2a) described above,

may be prepared by reacting an amidine compound of formula IIa, or asalt thereof (such as a hydrohalide salt, preferably a hydrochloride ora hydrobromide salt, or any other equivalent salt), wherein R₈, G₁, G₂,G₃, G₄, and G₅ are as defined above;

-   -   or alternatively, by reacting an alkyl carboximidothioate        compound of formula IIb, or a salt thereof (such as a        hydrohalide salt, preferably a hydrochloride or a hydrobromide        salt, or any other equivalent salt), wherein R₈, G₁, G₂, G₃, G₄,        and G₅ are as defined above, and in which R₉ is C₁₋₆alkyl; with        a hydrazide compound of formula IIIa, or a salt thereof, wherein        Q_(a) is a radical selected from the group consisting of formula        Q_(1a) to Q_(2a) described above, optionally in presence of a        base such as alkali metal carbonates, for example sodium        carbonate or potassium carbonate, in a solvent such as methanol,        ethanol, isopropanol, acetonitrile, pyridine, acetic acid,        N,N-dimethylformamide or N,N-dimethylacetamide, at temperatures        between 0 and 200° C., preferably between 50 and 180° C.,        optionally under microwave irradiation. The compounds of formula        IIa or IIb may be reacted with any configuration (E or Z, or any        mixture thereof) on the carbon-nitrogen double bond.

Compounds of formula IIIa, or a salt thereof, wherein Q_(a) is asdefined above, may be prepared in analogy to processes described abovein the context of the preparation of compounds of the formula III asdescribed in scheme 1.

Compounds of formula VI(a) and VIb(a), wherein Q_(a) and R₀₀ are asdefined above, are known compounds or can be prepared by known methods,described in the literature.

The subgroup of compounds of formula I, wherein R₈, G₁, G₂, G₃, G₄, andG₅ are as defined above and wherein R₇ is defined as Q₁, in which A, Q,X and R₁ are as defined above, may be defined as compounds of formulaI-Q₁. Compounds of formula I-Q₁, wherein X is SO or SO₂,

may be prepared by a Suzuki reaction (scheme 2), which involves forexample, reacting compounds of formula IX, wherein A, R₁, R₈, G₁, G₂,G₃, G₄, and G₅ are as defined above, and in which X is SO or SO₂, andwherein Xa is a leaving group like, for example, chlorine, bromine oriodine (preferably bromine), or an aryl- or alkylsulfonate such astrifluoromethanesulfonate, with compounds of formula X, wherein Q is asdefined above, and wherein Y_(b1) can be a boron-derived functionalgroup, such as for example B(OH)₂ or B(OR_(b1))₂ wherein R_(b1) can be aC₁-C₄alkyl group or the two groups OR_(b1) can form together with theboron atom a five membered ring, as for example a pinacol boronic ester.The reaction may be catalyzed by a palladium based catalyst, for exampletetrakis(triphenylphosphine)-palladium(0),(1,1′bis(diphenylphosphino)ferrocene)dichloro-palladium-dichloromethane(1:1 complex) orchloro(2-dicyclohexylphosphino-2′,4′,6′-triisopropyl-1,1′-biphenyl)[2-(2′-amino-1,1′-biphenyl)]palladium(II) (XPhos palladacycle), in presence of a base, like sodiumcarbonate, tripotassium phosphate or cesium fluoride, in a solvent or asolvent mixture, like, for example dioxane, acetonitrile,N,N-dimethyl-formamide, a mixture of 1,2-dimethoxyethane and water or ofdioxane/water, or of toluene/water, preferably under inert atmosphere.The reaction temperature can preferentially range from room temperatureto the boiling point of the reaction mixture, or the reaction may beperformed under microwave irradiation. Such Suzuki reactions are wellknown to those skilled in the art and have been reviewed, for example,in J. Orgmet. Chem. 576, 1999, 147-168.

Alternatively compounds of formula I-Q₁, wherein X is SO or SO₂, may beprepared by a Stille reaction between compounds of formula Xa, wherein Qis as defined above, and wherein Y_(b2) is a trialkyl tin derivative,preferably tri-n-butyl tin or tri-methyl-tin, and compounds of formulaIX, wherein A, R₁, R₈, G₁, G₂, G₃, G₄, and G₅ are as defined above, andin which X is SO or SO₂, and wherein Xa is a leaving group like, forexample, chlorine, bromine or iodine (preferably bromine), or an aryl-or alkylsulfonate such as trifluoromethanesulfonate. Such Stillereactions are usually carried out in the presence of a palladiumcatalyst, for example tetrakis(triphenylphosphine)palladium(0), orbis(triphenylphosphine) palladium(II) dichloride, in an inert solventsuch as N,N-dimethylformamide, acetonitrile, toluene or dioxane,optionally in the presence of an additive, such as cesium fluoride, orlithium chloride, and optionally in the presence of a further catalyst,for example copper(I)iodide. Such Stille couplings are also well knownto those skilled in the art, and have been described in for example J.Org. Chem., 2005, 70, 8601-8604, J. Org. Chem., 2009, 74, 5599-5602, andAngew. Chem. Int. Ed., 2004, 43, 1132-1136.

When Q is a five- to six-membered, aromatic, partially saturated orfully saturated ring system linked via a nitrogen atom to the ring whichcontains the group A, then compounds of formula I-Q₁, wherein X is SO orSO₂, may be prepared from compounds of formula IX, wherein A, R₁, R₈,G₁, G₂, G₃, G₄, and G₅ are as defined above, and in which X is SO orSO₂, and wherein Xa is a leaving group like, for example, chlorine,bromine or iodine (preferably bromine), or an aryl- or alkylsulfonatesuch as trifluoromethanesulfonate, by reaction with a heterocycle Q-H(which contains an appropriate NH functionality) Xaa, wherein Q is asdefined above, in the presence of a base, such as potassium carbonateK₂CO₃ or cesium carbonate Cs₂CO₃, optionally in the presence of a coppercatalyst, for example copper(I) iodide, with or without an additive suchas L-proline, N,N′-dimethylcyclohexane-1,2-diamine orN,N′-dimethylethylene-diamine, in an inert solvent such asN-methylpyrrolidone NMP or N,N-dimethylformamide DMF at temperaturesbetween 30-150° C., optionally under microwave irradiation. Such areaction (C—N Bond Formation) is illustrated below (scheme 3) for theheterocycle Q-H J-30b, wherein J30b and Rx are as defined above,

to give compounds of formula IX-(J-30b), a particular sub-group ofcompounds of formula IX, wherein A, R₁, R₈, G₁, G₂, G₃, G₄, and G₅ andRx are as previously defined.

Oxidation of compounds of formula IX, wherein A, R₁, R₈, G₁, G₂, G₃, G₄,and G₅ are as defined above, and in which X is S (sulfide), and whereinXa is a leaving group like, for example, chlorine, bromine or iodine(preferably bromine), or an aryl- or alkylsulfonate such astrifluoromethanesulfonate, with a suitable oxidizing agent, intocompounds of formula IX, wherein X is SO or SO₂ may be achieved underconditions already described above.

A large number of compounds of the formula X, Xa and Xaa arecommercially available or can be prepared by those skilled in the art.

Alternatively, compounds of formula I-Q₁, wherein X is SO or SO₂, may beprepared from compounds of formula IX, wherein X is S (sulfide) byinvolving the same chemistry as described above, but by changing theorder of the steps (i.e. by running the sequence IX (X is S) to I-Q₁ (Xis S) via Suzuki, Stille or C—N bond formation, followed by an oxidationstep to form I-Q₁ (X is SO or SO₂).

In the particular situation within scheme 2 when Q is an optionallysubstituted triazole linked via a nitrogen atom to the ring whichcontains the group A, then compounds of formula I-Q₁, wherein X is SO orSO₂, may be prepared from compounds of formula IX, wherein A, R₁, R₈,G₁, G₂, G₃, G₄, and G₅ are as defined above, and in which X is S, SO orSO₂, and wherein Xa is a leaving group like, for example, chlorine,bromine or iodine (preferably bromine), or an aryl- or alkylsulfonatesuch as trifluoromethanesulfonate, by reaction with an optionallysubstituted triazole Q-H (which contains an appropriate NHfunctionality) Xaa, wherein Q is N-linked triazolyl, in solvents such asalcohols (eg. methanol, ethanol, isopropanol, or higher boiling linearor branched alcohols), pyridine or acetic acid, optionally in thepresence of an additional base, such as potassium carbonate K₂CO₃ orcesium carbonate Cs₂CO₃, optionally in the presence of a coppercatalyst, for example copper(I) iodide, at temperatures between 30-180°C., optionally under microwave irradiation.

Compounds of formula IX, wherein A, R₁, R₈, G₁, G₂, G₃, G₄, and G₅ areas defined above, and in which X is S (sulfide), and wherein Xa is aleaving group like, for example, chlorine, bromine or iodine (preferablybromine), or an aryl- or alkylsulfonate such astrifluoromethanesulfonate,

may be prepared (scheme 4) by reacting an amidine compound of formulaIIa, or a salt thereof (such as a hydrohalide salt, preferably ahydrochloride or a hydrobromide salt, or any other equivalent salt),wherein R₈, G₁, G₂, G₃, G₄, and G₅ are as defined above;

or alternatively, by reacting an alkyl carboximidothioate compound offormula IIb, or a salt thereof (such as a hydrohalide salt, preferably ahydrochloride or a hydrobromide salt, or any other equivalent salt),wherein R₈, G₁, G₂, G₃, G₄, and G₅ are as defined above, and in which R₉is C₁₋₆alkyl; with a hydrazide compound of formula XVIII, or a saltthereof, wherein A and R₁ are as defined above, and in which X is S(sulfide), and wherein Xa is a leaving group like, for example,chlorine, bromine or iodine (preferably bromine), or an aryl- oralkylsulfonate such as trifluoromethanesulfonate, optionally in presenceof a base such as alkali metal carbonates, for example sodium carbonateor potassium carbonate, in a solvent such as methanol, ethanol,isopropanol, acetonitrile, pyridine, acetic acid, N,N-dimethylformamideor N,N-dimethylacetamide, at temperatures between 0 and 200° C.,preferably between 50 and 180° C., optionally under microwaveirradiation. The compounds of formula IIa or IIb may be reacted with anyconfiguration (E or Z, or any mixture thereof) on the carbon-nitrogendouble bond.

Compounds of formula XVIII, or a salt thereof, wherein A and R₁ are asdefined above, and in which X is S (sulfide), and wherein Xa is aleaving group like, for example, chlorine, bromine or iodine (preferablybromine), or an aryl- or alkylsulfonate such astrifluoromethanesulfonate,

may be prepared (scheme 5) in analogy to processes described above (seefor example preparation of compounds of the formula III, or scheme 1)from compounds of the formula XIII, via compounds of the formula XI,wherein A and R₁ are as defined above, and in which X is S (sulfide),and wherein Xa is a leaving group like, for example, chlorine, bromineor iodine (preferably bromine), or an aryl- or alkylsulfonate such astrifluoromethanesulfonate, and wherein R₀₀ is C₁-C₄alkyl, preferablymethyl or ethyl.

Compounds of formula XIII, wherein A and R₁ are as defined above, and inwhich X is S (sulfide), and wherein Xa is a leaving group like, forexample, chlorine, bromine or iodine (preferably bromine), or an aryl-or alkylsulfonate such as trifluoromethanesulfonate,

may be prepared (scheme 6) by hydrolysing compounds of formula XV,wherein X is S, and wherein A, R₁ and Xa are as defined above, forexample through heating in concentrated acid, such as concentratedhydrochloric acid HCl conc., optionally in the presence of an inertsolvent, such as ethers (for example tetrahydrofuran, ethylene glycoldimethyl ether, or 1,4-dioxane). Such hydrolysis conditions, andvariants thereof, are known to a person skilled in the art.

Compounds of formula XV, wherein X is S, and wherein A, R₁ and Xa are asdefined above, may be prepared by reacting compounds of formula XVI,wherein A and Xa are as defined above, and in which Xb is a leavinggroup such as, for example, a halogen (preferably fluorine, chlorine orbromine) or nitro, with a compound of formula VIII, or a salt thereofVIIIa, wherein R₁ is as defined in formula I, optionally in the presenceof a suitable base, such as alkali metal carbonates, for example sodiumcarbonate and potassium carbonate, or alkali metal hydrides such assodium hydride, or alkali metal hydroxides such as sodium hydroxide andpotassium hydroxide, optionally in the presence of a catalytic amount ofan additive, such as an ammonium salt (for example tetrabutylammoniumbromide TBAB), in an inert solvent at temperatures preferably between25-120° C. Examples of solvent to be used include ethers such as THF,ethylene glycol dimethyl ether, tert-butylmethyl ether, and 1,4-dioxane,aromatic hydrocarbons such as toluene and xylene, nitriles such asacetonitrile, polar aprotic solvents such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methyl-2-pyrrolidone or dimethyl sulfoxide, orwater. Examples of salts of the compound of formula VIII includecompounds of the formula VIIIa

R₁—S-M  (VIIIa),

wherein R₁ is as defined above and wherein M is, for example, sodium orpotassium.

Compounds of formula I-Q₁, wherein X is S, SO or SO₂,

may alternatively be prepared by a Suzuki reaction (scheme 7), whichinvolves for example, reacting compounds of formula XVII (or analogousboronic acids and esters of the formula XVII-Int), wherein A, R₁, R₈,G₁, G₂, G₃, G₄, and G₅ are as defined above, and in which X is S, SO orSO₂, with compounds of formula XX, wherein Q is as defined above, andwherein Xc is a leaving group like, for example, chlorine, bromine oriodine (preferably bromine), or an aryl- or alkylsulfonate such astrifluoromethanesulfonate. The reaction may be catalyzed by a palladiumbased catalyst, for example tetrakis(triphenylphosphine)-palladium(0),(1,1′bis(diphenylphosphino)ferrocene) dichloro-palladium-dichloromethane(1:1 complex) orchloro(2-dicyclohexylphosphino-2′,4′,6′-triisopropyl-1,1′-biphenyl)[2-(2′-amino-1,1′-biphenyl)]palladium(II)(XPhos palladacycle), in presence of a base, like sodium carbonate,tripotassium phosphate or cesium fluoride, in a solvent or a solventmixture, like, for example dioxane, acetonitrile, N,N-dimethylformamide,a mixture of 1,2-dimethoxy-ethane and water or of dioxane/water, or oftoluene/water, preferably under inert atmosphere. The reactiontemperature can preferentially range from room temperature to theboiling point of the reaction mixture, or the reaction may be performedunder microwave irradiation. Such Suzuki reactions are well known tothose skilled in the art and have been reviewed, for example, in J.Orgmet. Chem. 576, 1999, 147-168.

When Q is a five- to six-membered, aromatic, partially saturated orfully saturated ring system linked via a nitrogen atom to the ring whichcontains the group A, then compounds of formula I-Q₁, wherein X is S, SOor SO₂, may be prepared from compounds of formula XVII, wherein A, R₁,R₈, G₁, G₂, G₃, G₄, and G₅ are as defined above, and in which X is S, SOor SO₂, by reaction with a heterocycle Q-H (which contains anappropriate NH functionality) Xaa, wherein Q is as defined above. Thereaction, also known as Chan-Lam coupling (P. Y. S. Lam, C. G. Clark, S.Saubern, J. Adams, M. P. Winters, D. M. T. Chan, A. Combs, TetrahedronLett. 1998, 39, 2941), is commonly performed with one to two equivalentsof a base, like pyridine or triethylamine, in presence of one to twoequivalents of a copper derivative, like for example copper (II) acetateand under an oxygen-containing atmosphere. The reaction can be run in aninert solvent, like dichloromethane, dioxane or dimethylformamide,usually at or around room temperature.

Compounds of formula XVII, wherein A, R₁, R₈, G₁, G₂, G₃, G₄, and G₅ areas defined above, and in which X is S, SO or SO₂, may be prepared byreacting compounds of formula IX, wherein A, R₁, R₈, G₁, G₂, G₃, G₄, andG₅ are as defined above, and in which X is S, SO or SO₂, and wherein Xais a leaving group like, for example, chlorine, bromine or iodine(preferably bromine), or an aryl- or alkylsulfonate such astrifluoromethanesulfonate, with bispinacol diborane (Bpin)₂ underpalladium catalysis. Such an introduction of a pinacolborate functionalgroup can be performed in an aprotic solvent, such as dioxane, inpresence of a base, preferably a weak base, such as potassium acetateKOAc. [1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium(II), alsoknown as palladium dppf dichloride or Pd(dppf)Cl₂, is a common catalystfor this type of reaction. The temperature of the reaction is preferablyperformed between 0° C. and the boiling point of the reaction mixture,or the reaction may be performed under microwave irradiation.

The compounds of formula XVII-Int

wherein

R₁, R₈, G₁, G₂, G₃, G₄, G₅, X and A are as defined under formula Iabove, and Yb₃ is —B(OH)₂, —B(OR_(b2))₂, in which R_(b2) is a C₁-C₆alkylor Yb₃ is

(a 4,4,5,5-tetramethyl-1,3,2-dioxaborolane group), are novel, especiallydeveloped for the preparation of the compounds of formula I according tothe invention and therefore represent a further object of the invention.The preferences and preferred embodiments of the substituents of thecompounds of formula I are also valid for the compounds of formulaXVII-Int.

The subgroup of compounds of formula VIb(a), wherein R₀₀ are is asdefined above and wherein Q_(a) is defined as Q_(1a), in which A, Q andX₁₀ are as defined above, may be defined as compounds of formula XXI.Compounds of formula XXI,

may serve to prepare useful building blocks of formula XIX (scheme 8),wherein A, Q, R₁ and R₀₀ are as defined above, and in which X is S(sulfide), by utilizing reagent VIII or VIIIa under reaction conditionsthat have been already described above.

Compounds of formula XXI, wherein A, Q, X₁₀ and R₀₀ are as definedabove, may themselves be prepared from readily available compounds offormula XXII, wherein A, Xa, X₁₀ and R₀₀ are as defined above, involvingreagents X, Xa or Xaa under reaction conditions that have been alreadydescribed above.

Compounds of formula VII, wherein Qa is Qa₁, and in which A, Q and X₁₀are as defined above, and wherein R₈, G₁, G₂, G₃, G₄, and G₅ are asdefined above,

may alternatively be prepared (scheme 9) from compounds of formulaXXIII, wherein Xa is as defined above, and in which A and X₁₀ are asdefined above, and wherein R₈, G₁, G₂, G₃, G₄, and G₅ are as definedabove, involving reagents X, Xa or Xaa under reaction conditions thathave been already described above.

Compounds of formula XXIII, wherein A, Xa and X₁₀ are as defined above,and wherein R₈, G₁, G₂, G₃, G₄, and G₅ are as defined above, may beprepared by reacting an amidine compound of formula IIa, or a saltthereof (such as a hydrohalide salt, preferably a hydrochloride or ahydrobromide salt, or any other equivalent salt), wherein R₈, G₁, G₂,G₃, G₄, and G₅ are as defined above;

or alternatively, by reacting an alkyl carboximidothioate compound offormula IIb, or a salt thereof (such as a hydrohalide salt, preferably ahydrochloride or a hydrobromide salt, or any other equivalent salt),wherein R₈, G₁, G₂, G₃, G₄, and G₅ are as defined above, and in which R₉is C₁₋₆alkyl;

with a hydrazide compound of formula XXIV, or a salt thereof, wherein A,Xa and X₁₀ are as defined above, optionally in presence of a base suchas alkali metal carbonates, for example sodium carbonate or potassiumcarbonate, in a solvent such as methanol, ethanol, isopropanol,acetonitrile, pyridine, acetic acid, N,N-dimethylformamide orN,N-dimethylacetamide, at temperatures between 0 and 200° C., preferablybetween 50 and 180° C., optionally under microwave irradiation. Thecompounds of formula IIa or IIb may be reacted with any configuration (Eor Z, or any mixture thereof) on the carbon-nitrogen double bond.

Compounds of formula XXIV, or a salt thereof, wherein A, Xa and X₁₀ areas defined above, may be prepared by reacting a readily availablecompounds of formula XXII, wherein A, Xa, X₁₀ and R₀₀ are as definedabove, with hydrazine (or a salt thereof), possibly in form of ahydrate, preferably hydrazine monohydrate, under conditions that havebeen already described above.

The subgroup of compounds of formula I, wherein R₈, G₁, G₂, G₃, G₄, andG₅ are as defined above and wherein R₇ is defined as Q₂, in which A, Q,X and R₁ are as defined above, may be defined as compounds of formulaI-Q₂ (scheme 10).

The chemistry described previously in schemes 2 to 9 to access compoundsof formula I-Q₁, as well as relevant intermediates (see text,descriptions and preparation methods associated to schemes 2 to 9), maybe applied analogously for the preparation of compounds of formula I-Q₂,possibly by changing the order of certain steps in a sequence and byslightly adapting reaction conditions in a manner known to a personskilled in the art. Such a transposition is illustrated in scheme 10afor the preparation of compounds of formula I-Q₂ from intermediateXXII-p, wherein all substituent definitions mentioned previously arealso valid for the compounds shown.

Another such transposition is illustrated in scheme 10b, wherein allsubstituent definitions mentioned previously are also valid for thecompounds shown.

Compounds of formula I wherein Q is C₃-C₆cycloalkyl, mono- orpolysubstituted by substituents selected from the group consisting ofhalogen, cyano, C₁-C₄haloalkyl, and phenyl, may be prepared by methodsdescribed above. For the special case of compounds of formula I whereinQ is C₃-C₆cycloalkyl substituted by cyano (e.g. compounds Iaa) andC₁-C₄haloalkyl (e.g. compounds lad), the compounds can be prepared bythe methods shown in scheme 11.

As shown in scheme 11, treatment of compounds of formula IX, wherein Xis S, SO or SO₂ (in particular SO₂), and in which A, R₁, R₈, G₁, G₂, G₃,G₄, and G₅ are as defined above and wherein Xa is preferably halogen(even more preferably chlorine, bromine or iodine), withtrimethylsilyl-acetonitrile TMSCN, in the presence of zinc(II)fluorideZnF₂, and a palladium(0) catalyst such astris(dibenzylideneacetone)dipalladium(0)-chloroform adduct (Pd₂(dba)₃),with a ligand, for example Xantphos, in an inert solvent, such asN,N-dimethylformamide DMF at temperatures between 100-180° C.,optionally under microwave heating, leads to compounds of formula lab,wherein X is S, SO or SO₂ (in particular SO₂). Such chemistry has beendescribed in the literature, e.g. in Org. Lett. 16(24), 6314-6317, 2014.Compounds of formula lab can be treated with compounds of formula XXV,wherein Qx is a direct bond or is (CH₂)_(n) and n is 1, 2 or 3, and inwhich Xb₁ is a leaving group such as a halogen (preferably chlorine,bromine or iodine), in the presence of a base such as sodium hydride,potassium carbonate K₂CO₃, or cesium carbonate Cs₂CO₃, in an inertsolvent such as N,N-dimethyl-formamide DMF, acetone, or acetonitrile, attemperatures between 0-120° C., to give compounds of formula Iaa,wherein X is S, SO or SO₂ (in particular SO₂), and wherein A, R₁, R₈,G₁, G₂, G₃, G₄, and G₅ are as defined above and in which Qx is a directbond or is (CH₂)_(n) and n is 1, 2 or 3. Alternatively, compounds offormula Iaa can be prepared directly from compounds of formula IX bytreatment with compounds of formula XXVI, wherein Qx is as described inXXV, in presence of a catalyst such as Pd₂(dba)₃, with a ligand, such asBINAP, a strong base such as lithium hexamethyldisilazane LiHMDS, in aninert solvent such as tetrahydrofuran THF, at temperatures between30-80° C. Such chemistry has been described in, for example, J. Am.Chem. Soc. 127(45), 15824-15832, 2005.

Compounds of the formula Iaa may further be utilized for the preparationof compounds of formula lad (scheme 11). Indeed, compounds of formulaIaa, wherein X is S, SO or SO₂, and wherein A, R₁, R₈, G₁, G₂, G₃, G₄,and G₅ are as defined above and in which Qx is a direct bond or is(CH₂)_(n) and n is 1, 2 or 3, may be hydrolyzed, under conditions knownto a person skilled in the art (aqueous basic or acidic conditions, seee.g. scheme 6), to compounds of formula Iac, wherein X is S, SO or SO₂,and wherein A, R₁, R₈, G₁, G₂, G₃, G₄, and G₅ are as defined above andin which Qx is a direct bond or is (CH₂)_(n) and n is 1, 2 or 3.Treatment of compounds of formula Iac with reagents such as sulfurtetrafluoride SF₄ or Fluolead (4-tert-butyl-2,6-dimethyl phenylsulfurtrifluoride), optionally in the presence of hydrogen fluoride HF, attemperatures between 20-100° C., leads to compounds of formula lad,wherein X is S, SO or SO₂, and wherein A, R₁, R₈, G₁, G₂, G₃, G₄, and G₅are as defined above and in which Qx is a direct bond or is (CH₂)_(n)and n is 1, 2 or 3.

The compounds of formula (Iab)

wherein

R₁, R₈, G₁, G₂, G₃, G₄, G₅, X and A are as defined under formula Iabove, are novel, especially developed for the preparation of thecompounds of formula I according to the invention and thereforerepresent a further object of the invention. The preferences andpreferred embodiments of the substituents of the compounds of formula Iare also valid for the compounds of formula (Iab).

Compounds of formula I wherein Q is C₁-C₆haloalkylsulfanyl (e.g.compounds Iae and/or Iaf), C₁-C₆haloalkylsulfinyl andC₁-C₆haloalkylsulfonyl can be prepared by the methods shown in schemes12 and 13.

As shown in scheme 12, treatment of compounds of formula IX, wherein Xis S, SO or SO₂ (in particular S), and in which A, R₁, R₈, G₁, G₂, G₃,G₄, and G₅ are as defined above and wherein Xa is preferably halogen(even more preferably chlorine, bromine or iodine), with a bipyridinecopper reagent (bpy)CuSR_(F), wherein R_(F) is C₁-C₆haloalkyl, and inwhich bpy is bipyridyl, in an inert solvent such as acetonitrile, attemperatures between room temperature and 120° C., optionally undermicrowave heating, leads to compounds of formula Iae, wherein X is S, SOor SO₂ (in particular S), and in which A, R₁, R₈, G₁, G₂, G₃, G₄, and G₅are as defined above and wherein R_(F) is C₁-C₆haloalkyl. Such chemistryis known and has been described in the literature, for example, inAngew. Chem. Int. Ed. 2013, 52, 1548-1552. A preferred reagent for thistransformation is (bpy)CuSCF₃ (CAS 1413732-47-4) for the particularpreparation of compounds of formula Iae and Iaf, wherein R_(F) istrifluoromethyl.

Compounds of formula Iae, wherein X is S or SO, can be further oxidizedto, for example, compounds of formula Iaf, wherein X is SO or SO₂ (inparticular SO₂), and in which A, R₁, R₈, G₁, G₂, G₃, G₄, and G₅ are asdefined above and wherein R_(F) is C₁-C₆haloalkyl, by methods known tothose skilled in the art and described herein above.

Further adjustment of the oxidation state at sulfur centres can beaccomplished as shown in scheme 13 by methods known to those skilled inthe art. Thus, the compound of formula Iae, wherein X is S, can beoxidized to a compound of formula Iaf, wherein X is SO, by treating forexample with sodium periodate or m-chloroperbenzoic acid, in an inertsolvent such as dichloromethane and chloroform, alcohols such asmethanol and ethanol, acetic acid, water, and mixtures thereof. Theamount of the oxidant to be used in the reaction is generally 1 to 3moles, preferably 1 to 1.1 moles, relative to 1 mole of the presentcompound Iae. The reaction temperature of the reaction is generallywithin a range of 0° C. to room temperature.

The compound represented by the formula Iaf, wherein X is SO₂ can beproduced by reacting the compound of formula Iae, wherein X is S, in thepresence of an oxidant, such as m-chloroperbenzoic acid, in an inertsolvent. Examples of the solvent to be used in the reaction includealiphatic halogenated hydrocarbons such as dichloromethane andchloroform, alcohols such as methanol and ethanol, acetic acid, water,and mixtures thereof. Examples of the oxidant to be used in the reactioninclude m-chloroperbenzoic acid and hydrogen peroxide solution. Theamount of the oxidant to be used in the reaction is generally 1 to 4moles, preferably 2.1 moles, relative to 1 mole of the present compoundIae. The reaction temperature of the reaction is generally within arange of 0° C. to room temperature. The reaction may be conducted in thepresence of a catalyst. Examples of the catalyst to be used in thereaction include sodium tungstate. The SR_(F) group, wherein R_(F) isC₁-C₆haloalkyl, is more difficult to oxidize and so compounds of formulaIag and Iah generally require higher temperature with oxidants such asm-chloroperbenzoic acid or a hydrogen peroxide solution in the presenceof a catalyst, for example sodium tungstate. Solvent and oxidantequivalent are similar to the descriptions above (conditions: see scheme13). Those skilled in the art will appreciate that the degree andposition of oxidation will depend on such factors as equivalents ofoxidant and reaction temperature. Those skilled in the art will alsoappreciate that even if mixtures of products are formed, these can beseparated by crystallization or chromatographic techniques, and theposition and degree of oxidation can be determined by spectroscopicmethods such as mass spectroscopy, NMR techniques and ¹³C-¹H couplingconstants.

The chemistry described previously in schemes 11 to 13 to accesscompounds of formula I-Q₁, as well as relevant intermediates (see text,descriptions and preparation methods associated to schemes 11 to 13),may be applied analogously for the preparation of compounds of formulaI-Q₂, possibly by changing the order of certain steps in a sequence andby slightly adapting reaction conditions in a manner known to a personskilled in the art.

The reactants can be reacted in the presence of a base. Examples ofsuitable bases are alkali metal or alkaline earth metal hydroxides,alkali metal or alkaline earth metal hydrides, alkali metal or alkalineearth metal amides, alkali metal or alkaline earth metal alkoxides,alkali metal or alkaline earth metal acetates, alkali metal or alkalineearth metal carbonates, alkali metal or alkaline earth metaldialkylamides or alkali metal or alkaline earth metal alkylsilylamides,alkylamines, alkylenediamines, free or N-alkylated saturated orunsaturated cycloalkylamines, basic heterocycles, ammonium hydroxidesand carbocyclic amines. Examples which may be mentioned are sodiumhydroxide, sodium hydride, sodium amide, sodium methoxide, sodiumacetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide,potassium carbonate, potassium hydride, lithium diisopropylamide,potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine,diisopropylethylamine, triethylenediamine, cyclohexylamine,N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine,4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine,benzyltrimethylammonium hydroxide and 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU).

The reactants can be reacted with each other as such, i.e. withoutadding a solvent or diluent. In most cases, however, it is advantageousto add an inert solvent or diluent or a mixture of these. If thereaction is carried out in the presence of a base, bases which areemployed in excess, such as triethylamine, pyridine, N-methylmorpholineor N,N-diethylaniline, may also act as solvents or diluents.

The reaction is advantageously carried out in a temperature range fromapproximately −80° C. to approximately +140° C., preferably fromapproximately −30° C. to approximately +100° C., in many cases in therange between ambient temperature and approximately +80° C.

A compound of formula I can be converted in a manner known per se intoanother compound of formula I by replacing one or more substituents ofthe starting compound of formula I in the customary manner by (an)othersubstituent(s) according to the invention.

Depending on the choice of the reaction conditions and startingmaterials which are suitable in each case, it is possible, for example,in one reaction step only to replace one substituent by anothersubstituent according to the invention, or a plurality of substituentscan be replaced by other substituents according to the invention in thesame reaction step.

Salts of compounds of formula I can be prepared in a manner known perse. Thus, for example, acid addition salts of compounds of formula I areobtained by treatment with a suitable acid or a suitable ion exchangerreagent and salts with bases are obtained by treatment with a suitablebase or with a suitable ion exchanger reagent.

Salts of compounds of formula I can be converted in the customary mannerinto the free compounds I, acid addition salts, for example, bytreatment with a suitable basic compound or with a suitable ionexchanger reagent and salts with bases, for example, by treatment with asuitable acid or with a suitable ion exchanger reagent.

Salts of compounds of formula I can be converted in a manner known perse into other salts of compounds of formula I, acid addition salts, forexample, into other acid addition salts, for example by treatment of asalt of inorganic acid such as hydrochloride with a suitable metal saltsuch as a sodium, barium or silver salt, of an acid, for example withsilver acetate, in a suitable solvent in which an inorganic salt whichforms, for example silver chloride, is insoluble and thus precipitatesfrom the reaction mixture.

Depending on the procedure or the reaction conditions, the compounds offormula I, which have salt-forming properties can be obtained in freeform or in the form of salts.

The compounds of formula I and, where appropriate, the tautomersthereof, in each case in free form or in salt form, can be present inthe form of one of the isomers which are possible or as a mixture ofthese, for example in the form of pure isomers, such as antipodes and/ordiastereomers, or as isomer mixtures, such as enantiomer mixtures, forexample racemates, diastereomer mixtures or racemate mixtures, dependingon the number, absolute and relative configuration of asymmetric carbonatoms which occur in the molecule and/or depending on the configurationof non-aromatic double bonds which occur in the molecule; the inventionrelates to the pure isomers and also to all isomer mixtures which arepossible and is to be understood in each case in this sense hereinaboveand hereinbelow, even when stereochemical details are not mentionedspecifically in each case.

Diastereomer mixtures or racemate mixtures of compounds of formula I, infree form or in salt form, which can be obtained depending on whichstarting materials and procedures have been chosen can be separated in aknown manner into the pure diasteromers or racemates on the basis of thephysicochemical differences of the components, for example by fractionalcrystallization, distillation and/or chromatography.

Enantiomer mixtures, such as racemates, which can be obtained in asimilar manner can be resolved into the optical antipodes by knownmethods, for example by recrystallization from an optically activesolvent, by chromatography on chiral adsorbents, for examplehigh-performance liquid chromatography (HPLC) on acetyl cellulose, withthe aid of suitable microorganisms, by cleavage with specific,immobilized enzymes, via the formation of inclusion compounds, forexample using chiral crown ethers, where only one enantiomer iscomplexed, or by conversion into diastereomeric salts, for example byreacting a basic end-product racemate with an optically active acid,such as a carboxylic acid, for example camphor, tartaric or malic acid,or sulfonic acid, for example camphorsulfonic acid, and separating thediastereomer mixture which can be obtained in this manner, for exampleby fractional crystallization based on their differing solubilities, togive the diastereomers, from which the desired enantiomer can be setfree by the action of suitable agents, for example basic agents.

Pure diastereomers or enantiomers can be obtained according to theinvention not only by separating suitable isomer mixtures, but also bygenerally known methods of diastereoselective or enantioselectivesynthesis, for example by carrying out the process according to theinvention with starting materials of a suitable stereochemistry.

N-oxides can be prepared by reacting a compound of the formula I with asuitable oxidizing agent, for example the H₂O₂/urea adduct in thepresence of an acid anhydride, e.g. trifluoroacetic anhydride. Suchoxidations are known from the literature, for example from J. Med.Chem., 32 (12), 2561-73, 1989 or WO 00/15615.

It is advantageous to isolate or synthesize in each case thebiologically more effective isomer, for example enantiomer ordiastereomer, or isomer mixture, for example enantiomer mixture ordiastereomer mixture, if the individual components have a differentbiological activity.

The compounds of formula I and, where appropriate, the tautomersthereof, in each case in free form or in salt form, can, if appropriate,also be obtained in the form of hydrates and/or include other solvents,for example those which may have been used for the crystallization ofcompounds which are present in solid form.

The compounds according to the following Tables 1 to 12 below can beprepared according to the methods described above. The examples whichfollow are intended to illustrate the invention and show preferredcompounds of formula I.

Table 1:

This table discloses the 36 compounds 1.001 to 1.036 of the formulaI-1a:

wherein X₁ is S, and Q_(Rx), R₁₁, G₁, G₂, G₃, G₄ and G₅ are as definedbelow:

TABLE 1 Comp. No Q_(Rx) R₁₁ G₁ G₂ G₃ G₄ G₅ 1.001

—CH₂CH₃ N CH CH C(CF₃) CH 1.002

—CH₂CH₃ N CH CH C(CF₃) CH 1.003

—CH₂CH₃ N CH CH C(CF₃) CH 1.004

—CH₂CH₃ N CH CH C(CF₃) CH 1.005

—CH₂CH₃ N CH CH C(CF₃) CH 1.006

—CH₂CH₃ N CH CH C(CF₃) CH 1.007

—CH₂CH₃ N CH CH C(CF₃) CH 1.008

—CH₂CH₃ N CH CH C(CF₃) CH 1.009

—CH₂CH₃ N CH CH C(CF₃) CH 1.010

—CH₂CH₃ N CH CH C(CF₃) CH 1.011

—CH₂CH₃ N CH CH C(CF₃) CH 1.012

—CH₂CH₃ N CH CH C(CF₃) CH 1.013

—CH₂CH₃ N CH CH C(CF₃) CH 1.014

—CH₂CH₃ N CH CH C(CF₃) CH 1.015

—CH₂CH₃ N CH CH C(CF₃) CH 1.016

—CH₂CH₃ N CH CH C(CF₃) CH 1.017

—CH₂CH₃ N CH CH C(CF₃) CH 1.018

—CH₂CH₃ N CH CH C(CF₃) CH 1.019

—CH₂CH₃ N CH CH C(CF₃) CH 1.020

—CH₂CH₃ N CH CH C(CF₃) CH 1.021

—CH₂CH₃ N CH CH C(CF₃) CH 1.022

—CH₂CH₃ N CH CH C(CF₃) CH 1.023

—CH₂CH₃ N CH CH C(CF₃) CH 1.024

—CH₂CH₃ N CH CH C(CF₃) CH 1.025

—CH₂CH₃ N CH CH C(CF₃) CH 1.026

—CH₂CH₃ N CH CH C(CF₃) CH 1.027

—CH₂CH₃ N CH CH C(CF₃) CH 1.028

—CH₂CH₃ N CH CH C(CF₃) CH 1.029

—CH₂CH₃ N CH CH C(CF₃) CH 1.030

—CH₂CH₃ N CH N C(CF₃) CH 1.031

—CH₂CH₃ N CH N C(CF₃) CH 1.032

—CH₂CH₃ N CH N C(CF₃) CH 1.033

—CH₂CH₃ N CH N C(CF₃) CH 1.034

—CH₂CH₃ N CH N C(CF₃) CH 1.035

—CH₂CH₃ N CH N C(CF₃) CH 1.036

—CH₂CH₃ N CH N C(CF₃) CH

and the N-oxides of the compounds of Table 1.

Table 2:

This table discloses the 36 compounds 2.001 to 2.036 of the formulaI-1a, wherein X₁ is SO, and Q_(Rx), R₁₁, G₁, G₂, G₃, G₄ and G₅ are asdefined in Table 1.

Table 3:

This table discloses the 36 compounds 3.001 to 3.036 of the formulaI-1a, wherein X₁ is SO₂, and Q_(Rx), R₁₁, G₁, G₂, G₃, G₄ and G₅ are asdefined in Table 1.

Table 4:

This table discloses the 2 compounds 4.001 to 4.002 of the formula I-2a:

wherein X₂ is S, and Q_(Rx), R₁₂, G₁, G₂, G₃, G₄ and G₅ are as definedbelow:

TABLE 4 Comp. No Q_(Rx) R₁₂ G₁ G₂ G₃ G₄ G₅ 4.001

—CH₂CH₃ N CH CH C(CF₃) CH 4.002

—CH₂CH₃ N CH CH C(CF₃) CH

and the N-oxides of the compounds of Table 4.

Table 5:

This table discloses the 2 compounds 5.001 to 5.002 of the formula I-2a,wherein X₁ is SO, and Q_(Rx), R₁₂, G₁, G₂, G₃, G₄ and G₅ are as definedin Table 4.

Table 6:

This table discloses the 2 compounds 6.001 to 6.002 of the formula I-2a,wherein X₁ is SO₂, and Q_(Rx), R₁₂, G₁, G₂, G₃, G₄ and G₅ are as definedin Table 4.

Table 7:

This table discloses the 15 compounds 7.001 to 7.015 of the formulaI-3a:

wherein X₁ is S, and Q_(Rx), R₁₁, G₁, G₂, G₃, G₄ and G₅ are as definedbelow:

TABLE 7 Comp. No Q_(Rx) R₁₁ G₁ G₂ G₃ G₄ G₅ 7.001

—CH₂CH₃ N CH CH C(CF₃) CH 7.002

—CH₂CH₃ N CH CH C(CF₃) CH 7.003

—CH₂CH₃ N CH CH C(CF₃) CH 7.004

—CH₂CH₃ N CH CH C(CF₃) CH 7.005

—CH₂CH₃ N CH CH C(CF₃) CH 7.006

—CH₂CH₃ N CH CH C(CF₃) CH 7.007

—CH₂CH₃ N CH CH C(CF₃) CH 7.008

—CH₂CH₃ N CH CH C(CF₃) CH 7.009

—CH₂CH₃ N CH N C(CF₃) CH 7.010

—CH₂CH₃ N CH N C(CF₃) CH 7.011

—CH₂CH₃ N CH N C(CF₃) CH 7.012

—CH₂CH₃ N CH N C(CF₃) CH 7.013

—CH₂CH₃ N CH N C(CF₃) CH 7.014

—CH₂CH₃ N CH N C(CF₃) CH 7.015

—CH₂CH₃ N CH N C(CF₃) CH

and the N-oxides of the compounds of Table 7.

Table 8:

This table discloses the 15 compounds 8.001 to 8.015 of the formulaI-3a, wherein X₁ is SO, and Q_(Rx), R₁₁, G₁, G₂, G₃, G₄ and G₅ are asdefined in Table 7.

Table 9:

This table discloses the 15 compounds 9.001 to 9.015 of the formulaI-3a, wherein X₁ is SO₂, and Q_(Rx), R₁₁, G₁, G₂, G₃, G₄ and G₅ are asdefined in Table 7.

Table 10:

This table discloses the 2 compounds 10.001 to 10.002 of the formulaI-4a:

wherein X₂ is S, and Q_(Rx), R₁₂, G₁, G₂, G₃, G₄ and G₅ are as definedbelow:

TABLE 10 Comp. No Q_(Rx) R₁₂ G₁ G₂ G₃ G₄ G₅ 10.001

—CH₂CH₃ N CH CH C(CF₃) CH 10.002

—CH₂CH₃ N CH CH C(CF₃) CH

and the N-oxides of the compounds of Table 10.

Table 11:

This table discloses the 2 compounds 11.001 to 11.002 of the formulaI-4a, wherein X₂ is SO, and Q_(Rx), R₁₂, G₁, G₂, G₃, G₄ and G₅ are asdefined in Table 10.

Table 12:

This table discloses the 2 compounds 12.001 to 12.002 of the formulaI-4a, wherein X₂ is SO₂, and Q_(Rx), R₁₂, G₁, G₂, G₃, G₄ and G₅ are asdefined in Table 10.

The compounds of formula I according to the invention are preventivelyand/or curatively valuable active ingredients in the field of pestcontrol, even at low rates of application, which have a very favorablebiocidal spectrum and are well tolerated by warm-blooded species, fishand plants. The active ingredients according to the invention actagainst all or individual developmental stages of normally sensitive,but also resistant, animal pests, such as insects or representatives ofthe order Acarina. The insecticidal or acaricidal activity of the activeingredients according to the invention can manifest itself directly, i.e. in destruction of the pests, which takes place either immediately oronly after some time has elapsed, for example during ecdysis, orindirectly, for example in a reduced oviposition and/or hatching rate, agood activity corresponding to a destruction rate (mortality) of atleast 50 to 60%.

Examples of the abovementioned animal pests are:

from the order Acarina, for example,

Acalitus spp, Aculus spp, Acaricalus spp, Aceria spp, Acarus siro,Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobiaspp, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae,Dermatophagoides spp, Eotetranychus spp, Eriophyes spp., Hemitarsonemusspp, Hyalomma spp., Ixodes spp., Olygonychus spp, Ornithodoros spp.,Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora,Phytonemus spp, Polyphagotarsonemus spp, Psoroptes spp., Rhipicephalusspp., Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp,Tarsonemus spp. and Tetranychus spp.;

from the order Anoplura, for example,

Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. andPhylloxera spp.;

from the order Coleoptera, for example,

Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp.,Aphodius spp, Astylus atromaculatus, Ataenius spp, Atomaria linearis,Chaetocnema tibialis, Cerotoma spp, Conoderus spp, Cosmopolites spp.,Cotinis nitida, Curculio spp., Cyclocephala spp, Dermestes spp.,Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp.,Heteronychus arator, Hypothenemus hampei, Lagria vilosa, LeptinotarsadecemLineata, Lissorhoptrus spp., Liogenys spp, Maecolaspis spp,Maladera castanea, Megascelis spp, Melighetes aeneus, Melolontha spp.,Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophagaspp, Phlyctinus spp., Popillia spp., Psylliodes spp., Rhyssomatusaubtilis, Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotrogaspp., Somaticus spp, Sphenophorus spp, Sternechus subsignatus, Tenebriospp., Tribolium spp. and Trogoderma spp.;

from the order Diptera, for example,

Aedes spp., Anopheles spp, Antherigona soccata, Bactrocea oleae, Bibiohortulanus, Bradysia spp, Calliphora erythrocephala, Ceratitis spp.,Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp,Drosophila melanogaster, Fannia spp., Gastrophilus spp., Geomyzatripunctata, Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyzaspp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp.,Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp.,Rhagoletis spp, Rivelia quadrifasciata, Scatella spp, Sciara spp.,Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.;

from the order Hemiptera, for example,

Acanthocoris scabrator, Acrosternum spp, Adelphocoris lineolatus,Amblypelta nitida, Bathycoelia thalassina, Blissus spp, Cimex spp.,Clavigralla tomentosicollis, Creontiades spp, Distantiella theobroma,Dichelops furcatus, Dysdercus spp., Edessa spp, Euchistus spp., Eurydemapulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus,Leptocorisa spp., Lygus spp, Margarodes spp, Murgantia histrionic,Neomegalotomus spp, Nesidiocoris tenuis, Nezara spp., Nysius simulans,Oebalus insularis, Piesma spp., Piezodorus spp, Rhodnius spp.,Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp.,Thyanta spp, Triatoma spp., Vatiga illudens;

Acyrthosium pisum, Adalges spp, Agalliana ensigera, Agonoscenatargionii, Aleurodicus spp, Aleurocanthus spp, Aleurolobus barodensis,Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula,Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., Aspidiotusspp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp,Brachycaudus spp, Brevicoryne brassicae, Cacopsylla spp, Cavariellaaegopodii Scop., Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalusdictyospermi, Cicadella spp, Cofana spectra, Cryptomyzus spp, Cicadulinaspp, Coccus hesperidum, Dalbulus maidis, Dialeurodes spp, Diaphorinacitri, Diuraphis noxia, Dysaphis spp, Empoasca spp., Eriosoma larigerum,Erythroneura spp., Gascardia spp., Glycaspis brimblecombei, Hyadaphispseudobrassicae, Hyalopterus spp, Hyperomyzus pallidus, Idioscopusclypealis, Jacobiasca lybica, Laodelphax spp., Lecanium corni,Lepidosaphes spp., Lopaphis erysimi, Lyogenys maidis, Macrosiphum spp.,Mahanarva spp, Metcalfa pruinosa, Metopolophium dirhodum, Myndus crudus,Myzus spp., Neotoxoptera sp, Nephotettix spp., Nilaparvata spp.,Nippolachnus piri Mats, Odonaspis ruthae, Oregma lanigera Zehnter,Parabemisia myricae, Paratrioza cockerelli, Parlatoria spp., Pemphigusspp., Peregrinus maidis, Perkinsiella spp, Phorodon humuli, Phylloxeraspp, Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp.,Pseudatomoscelis seriatus, Psylla spp., Pulvinaria aethiopica,Quadraspidiotus spp., Quesada gigas, Recilia dorsalis, Rhopalosiphumspp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp.,Sogatella furcifera, Spissistilus festinus, Tarophagus Proserpina,Toxoptera spp, Trialeurodes spp, Tridiscus sporoboli, Trionymus spp,Trioza erytreae, Unaspis citri, Zygina flammigera, Zyginidiascutellaris;

from the order Hymenoptera, for example,

Acromyrmex, Arge spp, Atta spp., Cephus spp., Diprion spp., Diprionidae,Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis,Neodiprion spp., Pogonomyrmex spp, Slenopsis invicta, Solenopsis spp.and Vespa spp.;

from the order Isoptera, for example,

Coptotermes spp, Corniternes cumulans, Incisitermes spp, Macrotermesspp, Mastotermes spp, Microtermes spp, Reticulitermes spp.; Solenopsisgeminate

from the order Lepidoptera, for example,

Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabamaargillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp.,Argyresthia spp, Argyrotaenia spp., Autographa spp., Bucculatrixthurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis,Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysiaambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp.,Coleophora spp., Colias lesbia, Cosmophila flava, Crambus spp,Crocidolomia binotalis, Cryptophlebia leucotreta, Cydalima perspectalis,Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea,Earias spp., Eldana saccharina, Ephestia spp., Epinotia spp, Estigmeneacrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella,Euproctis spp., Euxoa spp., Feltia jaculiferia, Grapholita spp., Hedyanubiferana, Heliothis spp., Hellula undalis, Herpetogramma spp,Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus,Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostegebifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestrabrassicae, Manduca sexta, Mythimna spp, Noctua spp, Operophtera spp.,Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp.,Panolis flammea, Papaipema nebris, Pectinophora gossypiela,Perileucoptera coffeella, Pseudaletia unipuncta, Phthorimaeaoperculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp.,Pseudoplusia spp, Rachiplusia nu, Richia albicosta, Scirpophaga spp.,Sesamia spp., Sparganothis spp., Spodoptera spp., Sylepta derogate,Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tutaabsoluta, and Yponomeuta spp.;

from the order Mallophaga, for example,

Damalinea spp. and Trichodectes spp.;

from the order Orthoptera, for example,

Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae,Locusta spp., Neocurtilla hexadactyla, Periplaneta spp., Scapteriscusspp, and Schistocerca spp.;

from the order Psocoptera, for example,

Liposcelis spp.;

from the order Siphonaptera, for example,

Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis;

from the order Thysanoptera, for example,

Calliothrips phaseoli, Frankliniella spp., Heliothrips spp,Hercinothrips spp., Parthenothrips spp, Scirtothrips aurantii,Sericothrips variabilis, Taeniothrips spp., Thrips spp;

from the order Thysanura, for example, Lepisma saccharina.

The active ingredients according to the invention can be used forcontrolling, i. e. containing or destroying, pests of the abovementionedtype which occur in particular on plants, especially on useful plantsand ornamentals in agriculture, in horticulture and in forests, or onorgans, such as fruits, flowers, foliage, stalks, tubers or roots, ofsuch plants, and in some cases even plant organs which are formed at alater point in time remain protected against these pests.

Suitable target crops are, in particular, cereals, such as wheat,barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodderbeet; fruit, for example pomaceous fruit, stone fruit or soft fruit,such as apples, pears, plums, peaches, almonds, cherries or berries, forexample strawberries, raspberries or blackberries; leguminous crops,such as beans, lentils, peas or soya; oil crops, such as oilseed rape,mustard, poppies, olives, sunflowers, coconut, castor, cocoa or groundnuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants,such as cotton, flax, hemp or jute; citrus fruit, such as oranges,lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce,asparagus, cabbages, carrots, onions, tomatoes, potatoes or bellpeppers; Lauraceae, such as avocado, Cinnamonium or camphor; and alsotobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines,hops, the plantain family and latex plants.

The compositions and/or methods of the present invention may be alsoused on any ornamental and/or vegetable crops, including flowers,shrubs, broad-leaved trees and evergreens.

For example the invention may be used on any of the following ornamentalspecies: Ageratum spp., Alonsoa spp., Anemone spp., Anisodonteacapsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp.(e.g. B. elatior, B. semperflorens, B. tubéreux), Bougainvillea spp.,Brachycome spp., Brassica spp. (ornamental), Calceolaria spp., Capsicumannuum, Catharanthus roseus, Canna spp., Centaurea spp., Chrysanthemumspp., Cineraria spp. (C. maritime), Coreopsis spp., Crassula coccinea,Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis,Dorotheantus spp., Eustoma grandiflorum, Forsythia spp., Fuchsia spp.,Geranium gnaphalium, Gerbera spp., Gomphrena globosa, Heliotropium spp.,Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp.,Hypoestes phyllostachya, Impatiens spp. (I. Walleriana), Iresines spp.,Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus,Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp., Nemesiaspp., Tagetes spp., Dianthus spp. (carnation), Canna spp., Oxalis spp.,Bellis spp., Pelargonium spp. (P. peltatum, P. Zonale), Viola spp.(pansy), Petunia spp., Phlox spp., Plecthranthus spp., Poinsettia spp.,Parthenocissus spp. (P. quinquefolia, P. tricuspidata), Primula spp.,Ranunculus spp., Rhododendron spp., Rosa spp. (rose), Rudbeckia spp.,Saintpaulia spp., Salvia spp., Scaevola aemola, Schizanthuswisetonensis, Sedum spp., Solanum spp., Surfinia spp., Tagetes spp.,Nicotinia spp., Verbena spp., Zinnia spp. and other bedding plants.

For example the invention may be used on any of the following vegetablespecies: Allium spp. (A. sativum, A. cepa, A. oschaninii, A. Porrum, A.ascalonicum, A. fistulosum), Anthriscus cerefolium, Apium graveolus,Asparagus officinalis, Beta vulgarus, Brassica spp. (B. Oleracea, B.Pekinensis, B. rapa), Capsicum annuum, Cicer arietinum, Cichoriumendivia, Cichorum spp. (C. intybus, C. endivia), Citrillus lanatus,Cucumis spp. (C. sativus, C. melo), Cucurbita spp. (C. pepo, C. maxima),Cyanara spp. (C. scolymus, C. cardunculus), Daucus carota, Foeniculumvulgare, Hypericum spp., Lactuca sativa, Lycopersicon spp. (L.esculentum, L. lycopersicum), Mentha spp., Ocimum basilicum,Petroselinum crispum, Phaseolus spp. (P. vulgaris, P. coccineus), Pisumsativum, Raphanus sativus, Rheum rhaponticum, Rosemarinus spp., Salviaspp., Scorzonera hispanica, Solanum melongena, Spinacea oleracea,Valerianella spp. (V. locusta, V. eriocarpa) and Vicia faba.

Preferred ornamental species include African violet, Begonia, Dahlia,Gerbera, Hydrangea, Verbena, Rosa, Kalanchoe, Poinsettia, Aster,Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum,Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia,Salvia, Hortensia, rosemary, sage, St. Johnswort, mint, sweet pepper,tomato and cucumber.

The active ingredients according to the invention are especiallysuitable for controlling Aphis craccivora, Diabrotica balteata,Heliothis virescens, Myzus persicae, Plutella xylostella and Spodopteralittoralis in cotton, vegetable, maize, rice and soya crops. The activeingredients according to the invention are further especially suitablefor controlling Mamestra (preferably in vegetables), Cydia pomonella(preferably in apples), Empoasca (preferably in vegetables, vineyards),Leptinotarsa (preferably in potatos) and Chilo supressalis (preferablyin rice).

The active ingredients according to the invention are especiallysuitable for controlling Aphis craccivora, Diabrotica balteata,Heliothis virescens, Myzus persicae, Plutella xylostella and Spodopteralittoralis in cotton, vegetable, maize, rice and soya crops. The activeingredients according to the invention are further especially suitablefor controlling Mamestra (preferably in vegetables), Cydia pomonella(preferably in apples), Empoasca (preferably in vegetables, vineyards),Leptinotarsa (preferably in potatos) and Chilo supressalis (preferablyin rice).

In a further aspect, the invention may also relate to a method ofcontrolling damage to plant and parts thereof by plant parasiticnematodes (Endoparasitic-, Semiendoparasitic- and Ectoparasiticnematodes), especially plant parasitic nematodes such as root knotnematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogynejavanica, Meloidogyne arenaria and other Meloidogyne species;cyst-forming nematodes, Globodera rostochiensis and other Globoderaspecies; Heterodera avenae, Heterodera glycines, Heterodera schachtii,Heterodera trifolii, and other Heterodera species; Seed gall nematodes,Anguina species; Stem and foliar nematodes, Aphelenchoides species;Sting nematodes, Belonolaimus longicaudatus and other Belonolaimusspecies; Pine nematodes, Bursaphelenchus xylophilus and otherBursaphelenchus species; Ring nematodes, Criconema species, Criconemellaspecies, Criconemoides species, Mesocriconema species; Stem and bulbnematodes, Ditylenchus destructor, Ditylenchus dipsaci and otherDitylenchus species; Awl nematodes, Dolichodorus species; Spiralnematodes, Heliocotylenchus multicinctus and other Helicotylenchusspecies; Sheath and sheathoid nematodes, Hemicycliophora species andHemicriconemoides species; Hirshmanniella species; Lance nematodes,Hoploaimus species; false rootknot nematodes, Nacobbus species; Needlenematodes, Longidorus elongatus and other Longidorus species; Pinnematodes, Pratylenchus species; Lesion nematodes, Pratylenchusneglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchusgoodeyi and other Pratylenchus species; Burrowing nematodes, Radopholussimilis and other Radopholus species; Reniform nematodes, Rotylenchusrobustus, Rotylenchus reniformis and other Rotylenchus species;Scutellonema species; Stubby root nematodes, Trichodorus primitivus andother Trichodorus species, Paratrichodorus species; Stunt nematodes,Tylenchorhynchus claytoni, Tylenchorhynchus dubius and otherTylenchorhynchus species; Citrus nematodes, Tylenchulus species; Daggernematodes, Xiphinema species; and other plant parasitic nematodespecies, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp.,Melinius spp., Punctodera spp., and Quinisulcius spp.

The compounds of the invention may also have activity against themolluscs. Examples of which include, for example, Ampullariidae; Arion(A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae(Bradybaena fruticum); Cepaea (C. hortensis, C. Nemoralis); ochlodina;Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum);Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H.itala, H. obvia); Helicidae Helicigona arbustorum); Helicodiscus; Helix(H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L.maximus, L. tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M.sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.

The term “crops” is to be understood as including also crop plants whichhave been so transformed by the use of recombinant DNA techniques thatthey are capable of synthesising one or more selectively acting toxins,such as are known, for example, from toxin-producing bacteria,especially those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, forexample, insecticidal proteins, for example insecticidal proteins fromBacillus cereus or Bacillus popilliae; or insecticidal proteins fromBacillus thuringiensis, such as δ-endotoxins, e.g. Cry1Ab, Cry1Ac,Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetativeinsecticidal proteins (Vip), e.g. Vip1, Vip2, Vip3 or Vip3A; orinsecticidal proteins of bacteria colonising nematodes, for examplePhotorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens,Xenorhabdus nematophilus; toxins produced by animals, such as scorpiontoxins, arachnid toxins, wasp toxins and other insect-specificneurotoxins; toxins produced by fungi, such as Streptomycetes toxins,plant lectins, such as pea lectins, barley lectins or snowdrop lectins;agglutinins; proteinase inhibitors, such as trypsin inhibitors, serineprotease inhibitors, patatin, cystatin, papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ionchannel blockers, such as blockers of sodium or calcium channels,juvenile hormone esterase, diuretic hormone receptors, stilbenesynthase, bibenzyl synthase, chitinases and glucanases.

In the context of the present invention there are to be understood byδ-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A,Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for exampleVip1, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncatedtoxins and modified toxins. Hybrid toxins are produced recombinantly bya new combination of different domains of those proteins (see, forexample, WO 02/15701). Truncated toxins, for example a truncated Cry1Ab,are known. In the case of modified toxins, one or more amino acids ofthe naturally occurring toxin are replaced. In such amino acidreplacements, preferably non-naturally present protease recognitionsequences are inserted into the toxin, such as, for example, in the caseof Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3Atoxin (see WO 03/018810). Examples of such toxins or transgenic plantscapable of synthesising such toxins are disclosed, for example, inEP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878and WO 03/052073.

The processes for the preparation of such transgenic plants aregenerally known to the person skilled in the art and are described, forexample, in the publications mentioned above. Cry1-type deoxyribonucleicacids and their preparation are known, for example, from WO 95/34656,EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plantstolerance to harmful insects. Such insects can occur in any taxonomicgroup of insects, but are especially commonly found in the beetles(Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera).

Transgenic plants containing one or more genes that code for aninsecticidal resistance and express one or more toxins are known andsome of them are commercially available. Examples of such plants are:YieldGard® (maize variety that expresses a Cry1Ab toxin); YieldGardRootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGardPlus® (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin);Starlink® (maize variety that expresses a Cry9C toxin); Herculex I®(maize variety that expresses a Cry1Fa2 toxin and the enzymephosphinothricin N-acetyltransferase (PAT) to achieve tolerance to theherbicide glufosinate ammonium); NuCOTN 33B® (cotton variety thatexpresses a Cry1Ac toxin); Bollgard I® (cotton variety that expresses aCry1Ac toxin); Bollgard II® (cotton variety that expresses a Cry1Ac anda Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and aCry1Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin);NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait),Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

Further examples of such transgenic crops are:

1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a truncated Cry1Ab toxin. Bt11 maize alsotransgenically expresses the enzyme PAT to achieve tolerance to theherbicide glufosinate ammonium.

2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a Cry1Ab toxin. Bt176 maize also transgenicallyexpresses the enzyme PAT to achieve tolerance to the herbicideglufosinate ammonium.

3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Maize which hasbeen rendered insect-resistant by transgenic expression of a modifiedCry3A toxin. This toxin is Cry3A055 modified by insertion of acathepsin-G-protease recognition sequence. The preparation of suchtransgenic maize plants is described in WO 03/018810.

4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863expresses a Cry3Bb1 toxin and has resistance to certain Coleopterainsects.

5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/ES/96/02.

6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C/NL/00/10. Geneticallymodified maize for the expression of the protein Cry1F for achievingresistance to certain Lepidoptera insects and of the PAT protein forachieving tolerance to the herbicide glufosinate ammonium.

7. NK603×MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue deTervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03.Consists of conventionally bred hybrid maize varieties by crossing thegenetically modified varieties NK603 and MON 810. NK603×MON 810 Maizetransgenically expresses the protein CP4 EPSPS, obtained fromAgrobacterium sp. strain CP4, which imparts tolerance to the herbicideRoundup® (contains glyphosate), and also a Cry1Ab toxin obtained fromBacillus thuringiensis subsp. kurstaki which brings about tolerance tocertain Lepidoptera, include the European corn borer.

Transgenic crops of insect-resistant plants are also described in BATS(Zentrum für Biosicherheit and Nachhaltigkeit, Zentrum BATS,Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch).

The term “crops” is to be understood as including also crop plants whichhave been so transformed by the use of recombinant DNA techniques thatthey are capable of synthesising antipathogenic substances having aselective action, such as, for example, the so-called“pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392 225).Examples of such antipathogenic substances and transgenic plants capableof synthesising such antipathogenic substances are known, for example,from EP-A-0 392 225, WO 95/33818 and EP-A-0 353 191. The methods ofproducing such transgenic plants are generally known to the personskilled in the art and are described, for example, in the publicationsmentioned above.

Antipathogenic substances which can be expressed by such transgenicplants include, for example, ion channel blockers, such as blockers forsodium and calcium channels, for example the viral KP1, KP4 or KP6toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases;the so-called “pathogenesis-related proteins” (PRPs; see e.g. EP-A-0 392225); antipathogenic substances produced by microorganisms, for examplepeptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818)or protein or polypeptide factors involved in plant pathogen defense(so-called “plant disease resistance genes”, as described in WO03/000906).

Further areas of use of the compositions according to the invention arethe protection of stored goods and store rooms and the protection of rawmaterials, such as wood, textiles, floor coverings or buildings, andalso in the hygiene sector, especially the protection of humans,domestic animals and productive livestock against pests of the mentionedtype.

The present invention also provides a method for controlling pests (suchas mosquitoes and other disease vectors; see alsohttp://www.who.int/malaria/vector_control/irs/en/). In one embodiment,the method for controlling pests comprises applying the compositions ofthe invention to the target pests, to their locus or to a surface orsubstrate by brushing, rolling, spraying, spreading or dipping. By wayof example, an IRS (indoor residual spraying) application of a surfacesuch as a wall, ceiling or floor surface is contemplated by the methodof the invention. In another embodiment, it is contemplated to applysuch compositions to a substrate such as non-woven or a fabric materialin the form of (or which can be used in the manufacture of) netting,clothing, bedding, curtains and tents.

In one embodiment, the method for controlling such pests comprisesapplying a pesticidally effective amount of the compositions of theinvention to the target pests, to their locus, or to a surface orsubstrate so as to provide effective residual pesticidal activity on thesurface or substrate. Such application may be made by brushing, rolling,spraying, spreading or dipping the pesticidal composition of theinvention. By way of example, an IRS application of a surface such as awall, ceiling or floor surface is contemplated by the method of theinvention so as to provide effective residual pesticidal activity on thesurface. In another embodiment, it is contemplated to apply suchcompositions for residual control of pests on a substrate such as afabric material in the form of (or which can be used in the manufactureof) netting, clothing, bedding, curtains and tents.

Substrates including non-woven, fabrics or netting to be treated may bemade of natural fibres such as cotton, raffia, jute, flax, sisal,hessian, or wool, or synthetic fibres such as polyamide, polyester,polypropylene, polyacrylonitrile or the like. The polyesters areparticularly suitable. The methods of textile treatment are known, e.g.WO 2008/151984, WO 2003/034823, U.S. Pat. No. 5,631,072, WO 2005/64072,WO2006/128870, EP 1724392, WO2005113886 or WO 2007/090739.

Further areas of use of the compositions according to the invention arethe field of tree injection/trunk treatment for all ornamental trees aswell all sort of fruit and nut trees.

In the field of tree injection/trunk treatment, the compounds accordingto the present invention are especially suitable against wood-boringinsects from the order Lepidoptera as mentioned above and from the orderColeoptera, especially against woodborers listed in the following tablesA and B:

TABLE A Examples of exotic woodborers of economic importance. FamilySpecies Host or Crop Infested Buprestidae Agrilus planipennis AshCerambycidae Anoplura glabripennis Hardwoods Scolytidae Xylosandruscrassiusculus Hardwoods X. mutilatus Hardwoods Tomicus piniperdaConifers

TABLE B Examples of native woodborers of economic importance. FamilySpecies Host or Crop Infested Buprestidae Agrilus anxius Birch Agriluspolitus Willow, Maple Agrilus sayi Bayberry, Sweetfern Agrilusvittaticolllis Apple, Pear, Cranberry, Serviceberry, HawthornChrysobothris femorata Apple, Apricot, Beech, Boxelder, Cherry,Chestnut, Currant, Elm, Hawthorn, Hackberry, Hickory, Horsechestnut,Linden, Maple, Mountain-ash, Oak, Pecan, Pear, Peach, Persimmon, Plum,Poplar, Quince, Redbud, Serviceberry, Sycamore, Walnut, Willow Texaniacampestris Basswood, Beech, Maple, Oak, Sycamore, Willow, Yellow-poplarCerambycidae Goes pulverulentus Beech, Elm, Nuttall, Willow, Black oak,Cherrybark oak, Water oak, Sycamore Goes tigrinus Oak Neoclytusacuminatus Ash, Hickory, Oak, Walnut, Birch, Beech, Maple, Easternhophornbeam, Dogwood, Persimmon, Redbud, Holly, Hackberry, Black locust,Honeylocust, Yellow-poplar, Chestnut, Osage-orange, Sassafras, Lilac,Mountain-mahogany, Pear, Cherry, Plum, Peach, Apple, Elm, Basswood,Sweetgum Neoptychodes trilineatus Fig, Alder, Mulberry, Willow, Netleafhackberry Oberea ocellata Sumac, Apple, Peach, Plum, Pear, Currant,Blackberry Oberea tripunctata Dogwood, Viburnum, Elm, Sourwood,Blueberry, Rhododendron, Azalea, Laurel, Poplar, Willow, MulberryOncideres cingulata Hickory, Pecan, Persimmon, Elm, Sourwood, Basswood,Honeylocust, Dogwood, Eucalyptus, Oak, Hackberry, Maple, Fruit treesSaperda calcarata Poplar Strophiona nitens Chestnut, Oak, Hickory,Walnut, Beech, Maple Scolytidae Corthylus columbianus Maple, Oak,Yellow-poplar, Beech, Boxelder, Sycamore, Birch, Basswood, Chestnut, ElmDendroctonus frontalis Pine Dryocoetes betulae Birch, Sweetgum, Wildcherry, Beech, Pear Monarthrum fasciatum Oak, Maple, Birch, Chestnut,Sweetgum, Blackgum, Poplar, Hickory, Mimosa, Apple, Peach, PinePhloeotribus liminaris Peach, Cherry, Plum, Black cherry, Elm, Mulberry,Mountain-ash Pseudopityophthorus pruinosus Oak, American beech, Blackcherry, Chickasaw plum, Chestnut, Maple, Hickory, Hornbeam, HophornbeamSesiidae Paranthrene simulans Oak, American chestnut Sanninauroceriformis Persimmon Synanthedon exitiosa Peach, Plum, Nectarine,Cherry, Apricot, Almond, Black cherry Synanthedon pictipes Peach, Plum,Cherry, Beach, Black Cherry Synanthedon rubrofascia Tupelo Synanthedonscitula Dogwood, Pecan, Hickory, Oak, Chestnut, Beech, Birch, Blackcherry, Elm, Mountain-ash, Viburnum, Willow, Apple, Loquat, Ninebark,Bayberry Vitacea polistiformis Grape

The present invention may be also used to control any insect pests thatmay be present in turfgrass, including for example beetles,caterpillars, fire ants, ground pearls, millipedes, sow bugs, mites,mole crickets, scales, mealybugs ticks, spittlebugs, southern chinchbugs and white grubs. The present invention may be used to controlinsect pests at various stages of their life cycle, including eggs,larvae, nymphs and adults.

In particular, the present invention may be used to control insect peststhat feed on the roots of turfgrass including white grubs (such asCyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp.(e.g. European chafer, R. majalis), Cotinus spp. (e.g. Green Junebeetle, C. nitida), Popillia spp. (e.g. Japanese beetle, P. japonica),Phyllophaga spp. (e.g. May/June beetle), Ataenius spp. (e.g. Blackturfgrass ataenius, A. spretulus), Maladera spp. (e.g. Asiatic gardenbeetle, M. castanea) and spp.), ground pearls (Margarodes spp.), molecrickets (tawny, southern, and short-winged; Scapteriscus spp.,Gryllotalpa africana) and leatherjackets (European crane fly, Tipulaspp.).

The present invention may also be used to control insect pests ofturfgrass that are thatch dwelling, including armyworms (such as fallarmyworm Spodoptera frugiperda, and common armyworm Pseudaletiaunipuncta), cutworms, billbugs (Sphenophorus spp., such as S. venatusverstitus and S. parvulus), and sod webworms (such as Crambus spp. andthe tropical sod webworm, Herpetogramma phaeopteralis).

The present invention may also be used to control insect pests ofturfgrass that live above the ground and feed on the turfgrass leaves,including chinch bugs (such as southern chinch bugs, Blissus insularis),Bermudagrass mite (Eriophyes cynodoniensis), rhodesgrass mealybug(Antonina graminis), two-lined spittlebug (Propsapia bicincta),leafhoppers, cutworms (Noctuidae family), and greenbugs. The presentinvention may also be used to control other pests of turfgrass such asred imported fire ants (Solenopsis invicta) that create ant mounds inturf.

In the hygiene sector, the compositions according to the invention areactive against ectoparasites such as hard ticks, soft ticks, mangemites, harvest mites, flies (biting and licking), parasitic fly larvae,lice, hair lice, bird lice and fleas.

Examples of such parasites are:

Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculusspp. and Phtirus spp., Solenopotes spp.

Of the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp. and Felicola spp.

Of the order Diptera and the suborders Nematocerina and Brachycerina,for example Aedes spp., Anopheles spp., Culex spp., Simulium spp.,Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp.,Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopotaspp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp.,Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossinaspp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp.,Hippobosca spp., Lipoptena spp. and Melophagus spp.

Of the order Siphonapterida, for example Pulex spp., Ctenocephalidesspp., Xenopsylla spp., Ceratophyllus spp.

Of the order Heteropterida, for example Cimex spp., Triatoma spp.,Rhodnius spp., Panstrongylus spp.

Of the order Blattarida, for example Blatta orientalis, Periplanetaamericana, Blattelagermanica and Supella spp.

Of the subclass Acaria (Acarida) and the orders Meta- and Meso-stigmata,for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp.,Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp.,Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp.,Pneumonyssus spp., Sternostoma spp. and Varroa spp.

Of the orders Actinedida (Prostigmata) and Acaridida (Astigmata), forexample Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobiaspp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp.,Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp.,Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp.,Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. andLaminosioptes spp.

The compositions according to the invention are also suitable forprotecting against insect infestation in the case of materials such aswood, textiles, plastics, adhesives, glues, paints, paper and card,leather, floor coverings and buildings.

The compositions according to the invention can be used, for example,against the following pests: beetles such as Hylotrupes bajulus,Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum,Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobiumcarpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctuslinearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis,Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychuscapucins, Heterobostrychus brunneus, Sinoxylon spec. and Dinoderusminutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas,Urocerus gigas taignus and Urocerus augur, and termites such asKalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermeslucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis andCoptotermes formosanus, and bristletails such as Lepisma saccharina.

The compounds according to the invention can be used as pesticidalagents in unmodified form, but they are generally formulated intocompositions in various ways using formulation adjuvants, such ascarriers, solvents and surface-active substances. The formulations canbe in various physical forms, e.g. in the form of dusting powders, gels,wettable powders, water-dispersible granules, water-dispersible tablets,effervescent pellets, emulsifiable concentrates, microemulsifiableconcentrates, oil-in-water emulsions, oil-flowables, aqueousdispersions, oily dispersions, suspo-emulsions, capsule suspensions,emulsifiable granules, soluble liquids, water-soluble concentrates (withwater or a water-miscible organic solvent as carrier), impregnatedpolymer films or in other forms known e.g. from the Manual onDevelopment and Use of FAO and WHO Specifications for Pesticides, UnitedNations, First Edition, Second Revision (2010). Such formulations caneither be used directly or diluted prior to use. The dilutions can bemade, for example, with water, liquid fertilisers, micronutrients,biological organisms, oil or solvents.

The formulations can be prepared e.g. by mixing the active ingredientwith the formulation adjuvants in order to obtain compositions in theform of finely divided solids, granules, solutions, dispersions oremulsions. The active ingredients can also be formulated with otheradjuvants, such as finely divided solids, mineral oils, oils ofvegetable or animal origin, modified oils of vegetable or animal origin,organic solvents, water, surface-active substances or combinationsthereof.

The active ingredients can also be contained in very fine microcapsules.Microcapsules contain the active ingredients in a porous carrier. Thisenables the active ingredients to be released into the environment incontrolled amounts (e.g. slow-release). Microcapsules usually have adiameter of from 0.1 to 500 microns. They contain active ingredients inan amount of about from 25 to 95% by weight of the capsule weight. Theactive ingredients can be in the form of a monolithic solid, in the formof fine particles in solid or liquid dispersion or in the form of asuitable solution. The encapsulating membranes can comprise, forexample, natural or synthetic rubbers, cellulose, styrene/butadienecopolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides,polyureas, polyurethane or chemically modified polymers and starchxanthates or other polymers that are known to the person skilled in theart. Alternatively, very fine microcapsules can be formed in which theactive ingredient is contained in the form of finely divided particlesin a solid matrix of base substance, but the microcapsules are notthemselves encapsulated.

The formulation adjuvants that are suitable for the preparation of thecompositions according to the invention are known per se. As liquidcarriers there may be used: water, toluene, xylene, petroleum ether,vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acidanhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone,butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkylesters of acetic acid, diacetone alcohol, 1,2-dichloropropane,diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycolabietate, diethylene glycol butyl ether, diethylene glycol ethyl ether,diethylene glycol methyl ether, N,N-dimethylformamide, dimethylsulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methylether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone,ethyl acetate, 2-ethylhexanol, ethylene carbonate,1,1,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyllactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycolmethyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glyceroldiacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamylacetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene,isopropyl myristate, lactic acid, laurylamine, mesityl oxide,methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyllaurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene,n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleicacid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid,propyl lactate, propylene carbonate, propylene glycol, propylene glycolmethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol,xylenesulfonic acid, paraffin, mineral oil, trichloroethylene,perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propyleneglycol methyl ether, diethylene glycol methyl ether, methanol, ethanol,isopropanol, and alcohols of higher molecular weight, such as amylalcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol,propylene glycol, glycerol, N-methyl-2-pyrrolidone and the like.

Suitable solid carriers are, for example, talc, titanium dioxide,pyrophillite clay, silica, attapulgite clay, kieselguhr, limestone,calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks,wheat flour, soybean flour, pumice, wood flour, ground walnut shells,lignin and similar substances.

A large number of surface-active substances can advantageously be usedin both solid and liquid formulations, especially in those formulationswhich can be diluted with a carrier prior to use. Surface-activesubstances may be anionic, cationic, non-ionic or polymeric and they canbe used as emulsifiers, wetting agents or suspending agents or for otherpurposes. Typical surface-active substances include, for example, saltsof alkyl sulfates, such as diethanolammonium lauryl sulfate; salts ofalkylarylsulfonates, such as calcium dodecylbenzenesulfonate;alkylphenol/alkylene oxide addition products, such as nonylphenolethoxylate; alcohol/alkylene oxide addition products, such astridecylalcohol ethoxylate; soaps, such as sodium stearate; salts ofalkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate;dialkyl esters of sulfosuccinate salts, such as sodiumdi(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitololeate; quaternary amines, such as lauryltrimethylammonium chloride,polyethylene glycol esters of fatty acids, such as polyethylene glycolstearate; block copolymers of ethylene oxide and propylene oxide; andsalts of mono- and di-alkylphosphate esters; and also further substancesdescribed e.g. in McCutcheon's Detergents and Emulsifiers Annual, MCPublishing Corp., Ridgewood N.J. (1981).

Further adjuvants that can be used in pesticidal formulations includecrystallisation inhibitors, viscosity modifiers, suspending agents,dyes, anti-oxidants, foaming agents, light absorbers, mixingauxiliaries, antifoams, complexing agents, neutralising or pH-modifyingsubstances and buffers, corrosion inhibitors, fragrances, wettingagents, take-up enhancers, micronutrients, plasticisers, glidants,lubricants, dispersants, thickeners, antifreezes, microbicides, andliquid and solid fertilisers.

The compositions according to the invention can include an additivecomprising an oil of vegetable or animal origin, a mineral oil, alkylesters of such oils or mixtures of such oils and oil derivatives. Theamount of oil additive in the composition according to the invention isgenerally from 0.01 to 10%, based on the mixture to be applied. Forexample, the oil additive can be added to a spray tank in the desiredconcentration after a spray mixture has been prepared. Preferred oiladditives comprise mineral oils or an oil of vegetable origin, forexample rapeseed oil, olive oil or sunflower oil, emulsified vegetableoil, alkyl esters of oils of vegetable origin, for example the methylderivatives, or an oil of animal origin, such as fish oil or beeftallow. Preferred oil additives comprise alkyl esters of C₈-C₂₂ fattyacids, especially the methyl derivatives of C₁₂-C₁₈ fatty acids, forexample the methyl esters of lauric acid, palmitic acid and oleic acid(methyl laurate, methyl palmitate and methyl oleate, respectively). Manyoil derivatives are known from the Compendium of Herbicide Adjuvants,10^(th) Edition, Southern Illinois University, 2010.

The inventive compositions generally comprise from 0.1 to 99% by weight,especially from 0.1 to 95% by weight, of compounds of the presentinvention and from 1 to 99.9% by weight of a formulation adjuvant whichpreferably includes from 0 to 25% by weight of a surface-activesubstance. Whereas commercial products may preferably be formulated asconcentrates, the end user will normally employ dilute formulations.

The rates of application vary within wide limits and depend on thenature of the soil, the method of application, the crop plant, the pestto be controlled, the prevailing climatic conditions, and other factorsgoverned by the method of application, the time of application and thetarget crop. As a general guideline compounds may be applied at a rateof from 1 to 2000 I/ha, especially from 10 to 1000 I/ha.

Preferred formulations can have the following compositions (weight %):

Emulsifiable Concentrates:

active ingredient: 1 to 95%, preferably 60 to 90%

surface-active agent: 1 to 30%, preferably 5 to 20%

liquid carrier: 1 to 80%, preferable 1 to 35%

Dusts:

active ingredient: 0.1 to 10%, preferably 0.1 to 5%

solid carrier: 99.9 to 90%, preferably 99.9 to 99%

Suspension Concentrates:

active ingredient: 5 to 75%, preferably 10 to 50%

water: 94 to 24%, preferably 88 to 30%

surface-active agent: 1 to 40%, preferably 2 to 30%

Wettable Powders:

active ingredient: 0.5 to 90%, preferably 1 to 80%

surface-active agent: 0.5 to 20%, preferably 1 to 15%

solid carrier: 5 to 95%, preferably 15 to 90%

Granules:

active ingredient: 0.1 to 30%, preferably 0.1 to 15%

solid carrier: 99.5 to 70%, preferably 97 to 85%

The following Examples further illustrate, but do not limit, theinvention.

Wettable powders a) b) c) active ingredients 25%  50% 75% sodiumlignosulfonate 5%  5% — sodium lauryl sulfate 3% —  5% sodiumdiisobutylnaphthalenesulfonate —  6% 10% phenol polyethylene glycolether —  2% — (7-8 mol of ethylene oxide) highly dispersed silicic acid5% 10% 10% Kaolin 62%  27% —

The combination is thoroughly mixed with the adjuvants and the mixtureis thoroughly ground in a suitable mill, affording wettable powders thatcan be diluted with water to give suspensions of the desiredconcentration.

Powders for dry seed treatment a) b) c) active ingredients 25% 50% 75%light mineral oil  5%  5%  5% highly dispersed silicic acid  5%  5% —Kaolin 65% 40% — Talcum — 20

The combination is thoroughly mixed with the adjuvants and the mixtureis thoroughly ground in a suitable mill, affording powders that can beused directly for seed treatment.

Emulsifiable concentrate active ingredients 10% octylphenol polyethyleneglycol ether (4-5 mol of ethylene  3% oxide) calciumdodecylbenzenesulfonate  3% castor oil polyglycol ether (35 mol ofethylene oxide)  4% Cyclohexanone 30% xylene mixture 50%

Emulsions of any required dilution, which can be used in plantprotection, can be obtained from this concentrate by dilution withwater.

Dusts a) b) c) Active ingredients  5%  6%  4% Talcum 95% — — Kaolin —94% — mineral filler — — 96%

Ready-for-use dusts are obtained by mixing the combination with thecarrier and grinding the mixture in a suitable mill. Such powders canalso be used for dry dressings for seed.

Extruder granules Active ingredients 15% sodium lignosulfonate  2%carboxymethylcellulose  1% Kaolin 82%

The combination is mixed and ground with the adjuvants, and the mixtureis moistened with water. The mixture is extruded and then dried in astream of air.

Coated granules Active ingredients 8% polyethylene glycol (mol. wt. 200)3% Kaolin 89% 

The finely ground combination is uniformly applied, in a mixer, to thekaolin moistened with polyethylene glycol. Non-dusty coated granules areobtained in this manner.

Suspension Concentrate

active ingredients 40% propylene glycol 10% nonylphenol polyethyleneglycol ether (15 mol of ethylene oxide)  6% Sodium lignosulfonate 10%carboxymethylcellulose  1% silicone oil (in the form of a 75% emulsionin water)  1% Water 32%

The finely ground combination is intimately mixed with the adjuvants,giving a suspension concentrate from which suspensions of any desireddilution can be obtained by dilution with water. Using such dilutions,living plants as well as plant propagation material can be treated andprotected against infestation by microorganisms, by spraying, pouring orimmersion.

Flowable Concentrate for Seed Treatment

active ingredients 40%  propylene glycol 5% copolymer butanol PO/EO 2%Tristyrenephenole with 10-20 moles EO 2% 1,2-benzisothiazolin-3-one0.5%  (in the form of a 20% solution in water) monoazo-pigment calciumsalt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2% Water 45.3%  

The finely ground combination is intimately mixed with the adjuvants,giving a suspension concentrate from which suspensions of any desireddilution can be obtained by dilution with water. Using such dilutions,living plants as well as plant propagation material can be treated andprotected against infestation by microorganisms, by spraying, pouring orimmersion.

Slow Release Capsule Suspension

28 parts of the combination are mixed with 2 parts of an aromaticsolvent and 7 parts of toluenediisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). Thismixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol,0.05 parts of a defoamer and 51.6 parts of water until the desiredparticle size is achieved. To this emulsion a mixture of 2.8 parts1,6-diaminohexane in 5.3 parts of water is added. The mixture isagitated until the polymerization reaction is completed. The obtainedcapsule suspension is stabilized by adding 0.25 parts of a thickener and3 parts of a dispersing agent.

The capsule suspension formulation contains 28% of the activeingredients. The medium capsule diameter is 8-15 microns. The resultingformulation is applied to seeds as an aqueous suspension in an apparatussuitable for that purpose.

Formulation types include an emulsion concentrate (EC), a suspensionconcentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), awater dispersible granule (WG), an emulsifiable granule (EG), anemulsion, water in oil (EO), an emulsion, oil in water (EW), amicro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable(OF), an oil miscible liquid (OL), a soluble concentrate (SL), anultra-low volume suspension (SU), an ultra-low volume liquid (UL), atechnical concentrate (TK), a dispersible concentrate (DC), a wettablepowder (WP), a soluble granule (SG) or any technically feasibleformulation in combination with agriculturally acceptable adjuvants.

PREPARATORY EXAMPLES

“Mp” means melting point in ° C. Free radicals represent methyl groups.¹H NMR measurements were recorded on a Brucker 400 MHz spectrometer,chemical shifts are given in ppm relevant to a TMS standard. Spectrameasured in deuterated solvents as indicated. Common abbreviations:aq=aqueous, min=minute, h=hour, sat=saturated, R=retention time,mCPBA=meta-chloroperoxybenzoic acid, MeOH=methanol, EtOH=ethanol,NaHCO₃=sodium hydrogen carbonate, Na₂CO₃=sodium carbonate, HCl=hydrogenchloride, CH₂Cl₂=dichloromethane, Et₃N=triethylamine,DMF=N,N-dimethylformamide. Either one of the LCMS and/or GCMS methodsbelow was used to characterize the compounds. The characteristic LCMSvalues obtained for each compound were the retention time (“Rt”,recorded in minutes) and the measured molecular ion (M+H)⁺.

LCMS and GCMS Methods: Method 1:

Spectra were recorded on a Mass Spectrometer from Waters (ZQ Singlequadrupole mass spectrometer) equipped with an electrospray source(Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range:30-60 V, Extractor: 2.00 V, Source Temperature: 150° C., DesolvationTemperature: 350° C., Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow: 650L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binarypump, heated column compartment and diode-array detector. Solventdegasser, binary pump, heated column compartment and diode-arraydetector. Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C.,DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH: gradient: 0 min 0% B, 100%A; 1.2-1.5 min 100% B; Flow (ml/min) 0.85.

Method 2:

Spectra were recorded on a Mass Spectrometer from Waters (SQD or ZQSingle quadrupole mass spectrometer) equipped with an electrospraysource (Polarity: positive or negative ions, Capillary: 3.00 kV, Conerange: 30-60 V, Extractor: 2.00 V, Source Temperature: 150° C.,Desolvation Temperature: 350° C., Cone Gas Flow: 0 L/Hr, Desolvation GasFlow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC fromWaters: Binary pump, heated column compartment and diode-array detector.Solvent degasser, binary pump, heated column compartment and diode-arraydetector. Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C.,DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH; gradient: 0 min 0% B, 100%A; 2.7-3.0 min 100% B; Flow (ml/min) 0.85.

Method 3:

GCMS analyses were performed on a Thermo Electron instrument where aTRACE GC ULTRA gas chromatograph (equipped with a Zebron Phenomenex ZB-5ms 15 m, diam: 0.25 mm, 0.25 μm column; H₂ flow 1.2 mL/min; tempinjector: 250° C.; temp detector: 220° C.; method: start at 70° C., then25° C./min until 320° C., hold 2 min at 320° C.) was linked to a DSQmass spectrometer characterizing the compounds by electron ionisation(EI).

Example P1: Preparation of5-(4-chlorophenyl)-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine(Compound P2) Step A-1: Preparation of methyl5-bromo-3-chloro-pyridine-2-carboxylate

To a slightly cloudy solution of 5-bromo-3-chloro-pyridine-2-carboxylicacid (60 g, 183.2 mmol) in dichloromethane (700 ml) was added dropwiseN,N-dimethylformamide (1 ml) and oxalylchloride (24.9 ml, 286.9 mmol).The cloudy solution was stirred for 3 hours at ambient temperature. Theresulting yellow solution was cooled to 10° C. and methanol (30.8 ml,761.3 mmol) was added dropwise to the mixture, keeping the temperaturebetween 15° and 20° C. The solution was stirred overnight at ambienttemperature. After neutralisation with an aqueous saturated solution ofsodium hydrogen carbonate, the organic layer was washed with brine,dried over sodium sulfate, filtrated and evaporated to give methyl5-bromo-3-chloro-pyridine-2-carboxylate (55 g) as a yellow solid, whichwas used without further purification. LCMS (method 2): 250/252/254(M+H)⁺, retention time 1.12 min.

Step A-2: Preparation of methyl3-chloro-5-(4-chlorophenyl)pyridine-2-carboxylate

A solution of methyl 5-bromo-3-chloro-pyridine-2-carboxylate (17.33 g,69.2 mmol), 4-chlorophenyl-boronic acid (11.36 g, 72.7 mmol), sodiumcarbonate (14.7 g, 138.4 mmol) in a mixture of 1,2-dimethoxyethane (500ml) and water (50 ml) was flushed with argon.Tetrakis(triphenylphosphine) palladium (4.0 g, 3.5 mmol) was added andthe mixture was stirred at 90° C. for 7 hours. More catalyst was added(0.5 g, 0.4 mmol) and the mixture was stirred another 2 hours at 90° C.After cooling, the reaction mixture was diluted with water and ethylacetate. The water phase was separated and washed twice with ethylacetate. The combined organic phases were dried over magnesium sulfateand evaporated under vacuum. The residue was submitted to flashchromatography to give methyl3-chloro-5-(4-chlorophenyl)pyridine-2-carboxylate (10.5 g). LCMS (method2): 282/284 (M+H)⁺, retention time 1.63 min.

Step A-3: Preparation of5-(4-chlorophenyl)-3-ethylsulfanyl-pyridine-2-carboxylic Acid

To a solution of methyl3-chloro-5-(4-chlorophenyl)pyridine-2-carboxylate (2.0 g, 7.1 mmol) in15 ml N,N-dimethylformamide, sodium ethanethiolate (3.3 g, 35 mmol) wasadded. The temperature rose to 40° C. and the reaction mixture wasstirred 1 hour at room temperature. The solution was diluted withtert-butyl methyl ether and was extracted with ice water. The aqueousphase was separated and neutralized with acetic acid and extracted withtert-butyl methyl ether and ethyl acetate. The combined organic layerswere dried over magnesium sulfate and evaporated under vacuum to give5-(4-chlorophenyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid (2.0 g)which was used without further purification. LCMS (method 2): 294/296(M+H)⁺, retention time 1.42 min.

Step A-4: Preparation of methyl5-(4-chlorophenyl)-3-ethylsulfanyl-pyridine-2-carboxylate

To a solution of5-(4-chlorophenyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid (220 mg,0.749 mmol) in methanol (5 ml) was added sulfuric acid (3 drops) and themixture stirred at reflux overnight. After cooling, the reaction mixturewas diluted with iced water and extracted with dichloromethane (5×). Thecombined organic layers were dried over sodium sulfate and concentratedunder reduced pressure. The residue was submitted to flash columnchromatography on silica (cyclohexane/ethyl acetate 1:1) to affordmethyl 5-(4-chlorophenyl)-3-ethylsulfanyl-pyridine-2-carboxylate (184mg) as a solid, mp 103-105° C. LCMS (method 2): 308/310 (M+H)⁺,retention time 1.70 min.

Step A-5: Preparation of5-(4-chlorophenyl)-3-ethylsulfanyl-pyridine-2-carbohydrazide

To a solution of methyl5-(4-chlorophenyl)-3-ethylsulfanyl-pyridine-2-carboxylate (184 mg, 0.598mmol) in methanol (2 ml) was added hydrazine monohydrate (0.0382 ml,0.777 mmol) and the mixture stirred at reflux for 3.5 hours. Aftercooling, the reaction mixture was concentrated under reduced pressure,the residue dissolved in dichloromethane, dried over sodium sulfate andevaporated to dryness to afford5-(4-chlorophenyl)-3-ethylsulfanyl-pyridine-2-carbohydrazide (145 mg) asa solid, mp 124-126° C. LCMS (method 1): 308/310 (M+H)⁺, retention time0.91 min. This material was used without further purification.

Step B-1: Preparation ofN,N′-dimethyl-4-(trifluoromethyl)pyridine-2-carboxamidine

To a solution of 4-(trifluoromethyl)pyridine-2-carbonitrile (1.7 g, 9.88mmol) in methanol (18 ml) was added sodium methoxide (25 wt % in MeOH)(2.1 g, 9.9 mmol, 2.3 ml) and the mixture stirred at room temperaturefor 3 hours. The reaction mixture was concentrated to dryness, theresidue suspended in methylamine (33 wt % in EtOH) (25 ml, 200.9 mmol)to which was added methylamine hydrochloride (6.7 g, 99.2 mmol). Thereaction mixture was heated in a closed high pressure vial at 90° C.overnight. After cooling, the mixture was concentrated and the residuetreated with dichloromethane, filtered and the filtrate evaporated underreduced pressure. This material was dissolved in diethyl ether, treatedwith a 2M hydrochloric acid solution in diethyl ether under cooling,stirred at 5-10° C. for 20 minutes, then diluted with water. The layerswere separated and the organic phase washed twice with water. Thecombined aqueous phases were basified to pH 12 by addition of an aqueous30% sodium hydroxide solution under cooling, and the product thoroughlyextracted with diethyl ether (4×). The combined organic layers weredried over sodium sulfate and concentrated under reduced pressure toafford N,N′-dimethyl-4-(trifluoromethyl)pyridine-2-carboxamidine as anoil (0.70 g), which was used without further purification. LCMS (method1): 218 (M+H)⁺, retention time 0.28 min. ¹⁹F-NMR (MeOD, ppm) −66.4.

Step C-1: Preparation of5-(4-chlorophenyl)-3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine(Compound P1)

A solution of5-(4-chlorophenyl)-3-ethylsulfanyl-pyridine-2-carbohydrazide (135 mg,0.439 mmol) andN,N′-dimethyl-4-(trifluoromethyl)pyridine-2-carboxamidine (95.3 mg,0.439 mmol) in methanol (3 ml) was heated at reflux temperatureovernight. After cooling, the reaction mixture was concentrated underreduced pressure, the residue dissolved in dichloromethane, dried oversodium sulfate and evaporated to dryness. The residue was purified oversilica by flash column chromatography (cyclohexane/ethyl acetate 3:1) toafford5-(4-chlorophenyl)-3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine(compound P1) as a solid (96 mg), mp 147-149° C. LCMS (method 2):476/478 (M+H)⁺, retention time 1.97 min. ¹H-NMR (CDCl₃, ppm) 1.36 (3H),3.03 (2H), 4.18 (3H), 7.51 (2H), 7.58 (3H), 7.89 (1H), 8.70 (1H), 8.73(1H), 8.87 (1H).

Step C-2: Preparation of5-(4-chlorophenyl)-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine(Title Compound P2)

To a solution of5-(4-chlorophenyl)-3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine(65 mg, 0.137 mmol) in dichloromethane (2 ml) at 10° C. was added mCPBA(75 wt % in water) (66 mg, 0.287 mmol, 75%) in one portion and themixture was stirred at 10° C. for 2 hours. The reaction mixture wasdiluted with tert-butyl methyl ether, washed successively with sat.aqueous sodium hydrogen carbonate (4×), a sat. aqueous sodium sodiumbisulfite solution (4×) and brine, dried over sodium sulfate andconcentrated under reduced pressure. The residue was purified oversilica by flash column chromatography (cyclohexane/ethyl acetate 3:1) toafford5-(4-chlorophenyl)-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine(title compound P2) as a solid (32 mg), mp 234-235° C. LCMS (method 2):508/510 (M+H)⁺, retention time 1.81 min. ¹H-NMR (CDCl₃, ppm) 1.40 (3H),3.86 (2H), 4.10 (3H), 7.56 (2H), 7.60 (1H), 7.67 (2H), 8.66 (1H), 8.72(1H), 8.87 (1H), 9.18 (1H).

Example P2: Preparation of3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-pyrazol-1-yl-pyridine(Compound P4) Step A-1: Preparation of5-bromo-3-chloro-pyridine-2-carbohydrazide

Obtained from methyl 5-bromo-3-chloro-pyridine-2-carboxylate (34 g,135.7 mmol) and hydrazine hydrate (8.75 ml, 176.5 mmol) in methanol (350ml) according to procedure Example P1, step A-5. The mixture was stirredat reflux temperature for 4 hours. The solid residue obtained afterworkup was suspended in diethyl ether, filtered, the solid washed withcold diethyl ether and dried in vacuo to afford5-bromo-3-chloro-pyridine-2-carbohydrazide (32.1 g) as a solid, mp146-148° C. LCMS (method 2): 250/252/254 (M+H)⁺; retention time: 0.47min. ¹H-NMR (DMSO-d₆, ppm) 4.59 (br s, 2H), 8.45 (s, 1H), 8.68 (s, 1H),9.77 (br s, 1H).

Step B-1: Preparation of5-bromo-3-chloro-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine

Obtained from 5-bromo-3-chloro-pyridine-2-carbohydrazide (554 mg, 2.21mmol) and N,N′-dimethyl-4-(trifluoromethyl)pyridine-2-carboxamidine (480mg, 2.21 mmol) in methanol (4 ml) according to procedure Example P1,step C-1. The mixture was stirred at reflux overnight. Flashchromatography purification (cyclohexane/ethyl acetate 4:1) afforded5-bromo-3-chloro-2-[4-methyl-5-[4-(trifluoro-methyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine(560 mg) as a solid, mp 152-154° C. LCMS (method 2): 418/420/422 (M+H)⁺;retention time: 1.53 min. ¹H-NMR (CDCl₃, ppm) 4.10 (s, 3H), 7.60 (d,1H), 8.13 (d, 1H), 8.70 (s, 1H), 8.75 (d, 1H), 8.87 (d, 1H).

Step B-2: Preparation of3-chloro-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-pyrazol-1-yl-pyridine

To a solution of5-bromo-3-chloro-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine(250 mg, 0.597 mmol) and 1H-pyrazole (44.7 mg, 0.657 mmol) inN,N-dimethylformamide (2 ml) under argon was added copper(I) iodide (5.7mg, 0.030 mmol), N,N′-dimethylethylenediamine (5.3 mg, 6.36 μl, 0.060mmol) and potassium carbonate (16.5 mg, 0.119 mmol). The mixture wasstirred at 100° C. for 4 hours. After cooling, the reaction mixture wasdiluted with ethyl acetate and filtered over diatomaceous earth (Hyflo).The filtrate was washed with water (3×), dried over sodium sulfate andconcentrated in vacuo. The residue was purified over silica by flashcolumn chromatography (cyclohexane/ethyl acetate 4:1) to afford3-chloro-2-[4-methyl-5-[4-(trifluoro-methyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-pyrazol-1-yl-pyridineas a solid (123 mg), mp 160-162° C. LCMS (method 2): 406/408 (M+H)⁺;retention time: 1.43 min. ¹H-NMR (CDCl₃, ppm) 4.12 (s, 3H), 6.61 (t,1H), 7.60 (d, 1H), 7.85 (d, 1H), 8.08 (d, 1H), 8.36 (d, 1H), 8.72 (s,1H), 8.88 (d, 1H), 9.08 (d, 1H).

Step B-3: Preparation of3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-pyrazol-1-yl-pyridine(Compound P3)

To a solution of3-chloro-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-pyrazol-1-yl-pyridine(123 mg, 0.303 mmol) in N,N-dimethylformamide (2.5 ml) at 10° C. wasadded sodium ethanethiolate (38.6 mg, 0.458 mmol) in one portion. Thereaction mixture was stirred at 50° C. overnight, then concentrated todryness under reduced pressure. The residue was diluted with ethylacetate and water, the layers separated, the organic phase washed withwater (3×), dried over sodium sulfate and concentrated in vacuo. Thesolid residue was stirred in diethyl ether, filtered, washed with colddiethyl ether and dried in vacuo to afford3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-pyrazol-1-yl-pyridine(compound P3) as a solid (101 mg), mp 121-123° C. LCMS (method 2): 432(M+H)⁺; retention time: 1.54 min. ¹H-NMR (CDCl₃, ppm) 1.39 (t, 3H), 3.06(q, 2H), 4.16 (s, 3H), 6.59 (t, 1H), 7.58 (d, 1H), 7.83 (d, 1H), 8.07(d, 1H), 8.19 (d, 1H), 8.72 (s, 1H), 8.83 (d, 1H), 8.87 (d, 1H).

Step B-4: Preparation of3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-pyrazol-1-yl-pyridine(Compound P4)

Obtained from3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-pyrazol-1-yl-pyridine(95 mg, 0.220 mmol) and mCPBA (106 mg, 0.462 mmol, 75%) indichloromethane (2.5 ml) according to procedure Example P1, step C-2.The mixture was stirred at room temperature overnight. Flashchromatography purification (cyclohexane/ethyl acetate 3:1) afforded3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-pyrazol-1-yl-pyridine(title compound P4) as a solid (52 mg), mp 174-176° C. LCMS (method 2):464 (M+H)⁺; retention time: 1.43 min. ¹H-NMR (CDCl₃, ppm) 1.41 (t, 3H),3.88 (q, 2H), 4.08 (s, 3H), 6.65 (t, 1H), 7.60 (d, 1H), 7.89 (d, 1H),8.15 (d, 1H), 8.71 (s, 1H), 8.77 (d, 1H), 8.87 (d, 1H), 9.47 (d, 1H).

Example P3: Preparation of3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-vinyl-pyridine(Compound P12) Step A-1: Preparation ofN-methyl-4-(trifluoromethyl)pyridine-2-carboxamide

To a solution of 4-(trifluoromethyl)pyridine-2-carboxylic acid (97%,10.0 g, 50.76 mmol) in dichloromethane (200 ml) was added dropwiseN,N-dimethylformamide (0.1 ml) and oxalyl chloride (5.66 ml, 66.00mmol). The reaction mixture was stirred at ambient temperatureovernight, then concentrated to dryness in vacuo to afford4-(trifluoromethyl)pyridine-2-carbonyl chloride (10.5 g) as a solid.

To methylamine (2M in tetrahydrofuran) (62.6 ml, 125.2 mmol) intetrahydrofuran (40 ml) at 0-5° C. was added triethylamine (10.4 ml,75.03 mmol), followed by a solution of4-(trifluoromethyl)pyridine-2-carbonyl chloride (10.5 g, 50.11 mmol,preparation above) in tetrahydrofuran (60 ml) dropwise. The mixture wasallowed to warm to room temperature, and stirred for 2 hours. Theresulting suspension was filtered, the solid residue washed with t-butylmethyl ether (3×) and the filtrate evaporated under reduced pressure.The residue was dissolved in t-butyl methyl ether, the organic phasewashed with water (3×) and brine, dried over sodium sulfate andconcentrated in vacuo. The crude material was diluted with t-butylmethyl ether, treated with activated charcoal, the mixture stirred for15 minutes and filtered. Evaporation of the filtrate in vacuo affordedN-methyl-4-(trifluoromethyl)pyridine-2-carboxamide as a solid (9.2 g),mp 60-62° C. This material was used without further purification. LCMS(method 2): 205 (M+H)⁺; retention time: 0.86 min. ¹H-NMR (CDCl₃, ppm)3.07 (d, 3H), 7.66 (d, 1H), 8.01 (br s, 1H), 8.45 (s, 1H), 8.74 (d, 1H).

Step A-2: Preparation ofN-methyl-4-(trifluoromethyl)pyridine-2-carbothioamide

To a solution of N-methyl-4-(trifluoromethyl)pyridine-2-carboxamide(32.5 g, 159.2 mmol) in pyridine (870 ml) was added phosphoruspentasulfide (42.5 g, 95.6 mmol) and the mixture was stirred at refluxtemperature for 5 hours. After cooling, the solvent was removed invacuo, the residue diluted with water and the aqueous phase extractedwith diethyl ether (3×). The combined organic layers were washed with awater/brine (1:1) solution (4×), dried over sodium sulfate andconcentrated under reduced pressure to affordN-methyl-4-(trifluoromethyl)pyridine-2-carbothioamide as a solid (30.9g), mp 69-70° C. This material was used without further purification.LCMS (method 2): 221 (M+H)⁺; retention time: 1.42 min. ¹H-NMR (CDCl₃,ppm) 3.43 (d, 3H), 7.66 (d, 1H), 8.68 (d, 1H), 8.96 (s, 1H), 10.14 (brs, 1H).

Step A-3: Preparation of ethylN-methyl-4-(trifluoromethyl)pyridine-2-carboximidothioate

To a solution of N-methyl-4-(trifluoromethyl)pyridine-2-carbothioamide(10.2 g, 46.32 mmol) in ethanol (200 ml) was added sodium ethoxide (21wt % in EtOH) (15.2 g, 46.3 mmol, 17.3 ml) and the mixture was stirredat room temperature for 40 minutes. Iodoethane (14.5 g, 92.68 mmol, 7.49ml) was added and stirring continued at room temperature overnight. Thereaction mixture was concentrated in vacuo, diluted with t-butyl methylether, the organic phase washed successively with water (3×), a sat.aqueous sodium carbonate solution and brine, dried over sodium sulfateand evaporated under reduced pressure to afford ethylN-methyl-4-(trifluoromethyl)pyridine-2-carboximidothioate, as a liquid(10.4 g). This material was used without further purification LCMS(method 2): 249 (M+H)⁺; retention time: 1.20 min. ¹H-NMR (CDCl₃, ppm,major isomer) 1.15 (t, 3H), 2.87 (q, 2H), 3.53 (s, 3H), 7.55 (d, 1H),7.91 (s, 1H), 8.84 (d, 1H).

Step B-1: Preparation of 5-bromo-3-ethylsulfanyl-pyridine-2-carbonitrile

Under nitrogen atmosphere, a solution of5-bromo-3-fluoro-pyridine-2-carbonitrile (1.005 g, 5.00 mmol) in dryN,N-dimethylformamide (15 ml) was cooled to −50° C. and to this wasadded dropwise a freshly prepared solution of sodium ethanethiolate(0.429 g, 5.10 mmol) in dry N,N-dimethylformamide (5 ml). After stirringat −50° C. for 30 minutes, the cooling bath was removed and the mixturewas allowed to warm to room temperature. Water and brine were added andthe aqueous mixture was extracted with ethyl acetate. After separation,the organic layer was washed twice with brine, dried over sodium sulfateand concentrated. The crude product was purified over silica by flashcolumn chromatography (0 to 40% gradient of ethyl acetate in heptane) toafford the title compound (0.93 g) as a solid. GCMS (method 3): 242/244(M)⁺, retention time 6.33 min. ¹H-NMR (CDCl₃, ppm) 1.41 (3H), 3.06 (2H),7.82 (1H), 8.49 (1H).

Alternative preparation method: Under nitrogen atmosphere, a solution of5-bromo-3-nitro-pyridine-2-carbonitrile (45.35 g, 199 mmol) in dryN,N-dimethylformamide (500 ml) was cooled to −50° C. and to this wasadded dropwise a freshly prepared solution of sodium ethanethiolate(17.4 g, 207 mmol) in dry N,N-dimethylformamide (200 ml) (not acompletely clear solution). After complete addition, stirring wascontinued at −50° C. for 30 minutes. Water and brine were added and thecooling bath was removed. The aqueous mixture was extracted with ethylacetate. After separation, the water layer was extracted with ethylacetate once more. The combined the organic layers were washed twicewith brine, dried over sodium sulfate and concentrated. The crudeproduct was purified over silica by flash column chromatography (0 to25% gradient of ethyl acetate in heptane) to afford the title compound(33.9 g) as a solid. LCMS (method 1): 243/245 (M+H)⁺; retention time:0.95 min.

Step B-2: Preparation of 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylicAcid

A solution of 5-bromo-3-ethylsulfanyl-pyridine-2-carbonitrile (43 g, 170mmol, 1.0 eq.) in 800 ml aqueous hydrogen chloride HCl 32% was heated to60° C. overnight. Dioxane (100 ml) was added and the mixture was furtherstirred at 60° C. for 48 h. The reaction mixture was cooled to 0-5° C.,treated with an aqueous sodium hydroxide solution (NaOH 30%) until pH11and washed with 2×200 ml tert-butyl methyl ether. The water phase wasacidified with HCl 10% back to pH4, the resulting solid was filtrated,washed with water and dried in vacuo. LCMS (method 1): 262, 264 (M+H)⁺;retention time: 0.77 min. ¹H NMR (400 MHz, CDCl₃) δ ppm: 8.50 (s, 1H);8.06 (s, 1H); 3.03 (q, 2H); 1.24 (t, 3H).

Step B-3: Preparation of methyl5-bromo-3-ethylsulfanyl-pyridine-2-carboxylate

To a suspension of 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylic acid(15.0 g, 57.23 mmol) in methanol (350 ml) was added sulfuric acid (0.5ml) and the mixture stirred at reflux overnight. After cooling, thesolution was concentrated under reduced pressure. The residue wastriturated with diethyl ether (200 ml), the suspension filtered, thesolid washed with cold diethyl ether and dried in vacuo to afford methyl5-bromo-3-ethylsulfanyl-pyridine-2-carboxylate (13.9 g) as a solid, mp72-74° C. LCMS (method 1): 276/278 (M+H)⁺, retention time 0.98 min.¹H-NMR (CDCl₃, ppm) 1.42 (3H), 2.94 (2H), 4.00 (3H), 7.78 (1H), 8.46(1H).

Step B-4: Preparation of5-bromo-3-ethylsulfanyl-pyridine-2-carbohydrazide

To a solution of methyl 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylate(19.8 g, 71.70 mmol) in methanol (300 ml) was added hydrazinemonohydrate (4.62 ml, 93.2 mmol) and the mixture stirred at reflux for 4hours. After cooling, the reaction mixture was concentrated underreduced pressure, the residue suspended in diethyl ether, filtered andthe solid washed with cold diethyl ether and dried in vacuo to afford5-bromo-3-ethylsulfanyl-pyridine-2-carbohydrazide (17.2 g) as a solid,mp 136-138° C. LCMS (method 1): 276/278 (M+H)⁺, retention time 0.75 min.¹H-NMR (CDCl₃, ppm) 1.42 (3H), 2.91 (2H), 4.02 (2H), 7.75 (1H), 8.28(1H), 8.82 (1H).

Step C-1: Preparation of5-bromo-3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine

A solution of 5-bromo-3-ethylsulfanyl-pyridine-2-carbohydrazide (556 mg,2.014 mmol) and ethylN-methyl-4-(trifluoromethyl)pyridine-2-carboximidothioate (500 mg, 2.014mmol) in ethanol (5 ml) was heated in the microwave at 150° C. for 30minutes. After cooling, the reaction mixture was concentrated underreduced pressure and the residue purified over silica by flash columnchromatography (0-25% ethyl acetate gradient in cyclohexane) to afford5-bromo-3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoro-methyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridineas a solid (700 mg), mp 122-123° C. LCMS (method 1): 444/446 (M+H)⁺,retention time 1.04 min. ¹H-NMR (CDCl₃, ppm) 1.36 (3H), 2.97 (2H), 4.14(3H), 7.58 (1H), 7.86 (1H), 8.55 (1H), 8.70 (1H), 8.87 (1H).

Alternative preparation method: To a solution of ethylN-methyl-4-(trifluoromethyl)pyridine-2-carboximidothioate (3.0 g,estimated 90%, 10.88 mmol) in pyridine (12 ml) which was purged withargon for 10 minutes was added5-bromo-3-ethylsulfanyl-pyridine-2-carbohydrazide (3.0 g, 10.88 mmol).The mixture was heated in the microwave at 180° C. for 40 minutes. Aftercooling, the reaction mixture was poured into ice-water, stirred for 10minutes, the suspension filtered and the solid washed with cold water.This solid was dissolved in dichloromethane, the solution dried oversodium sulfate and concentrated to dryness under reduced pressure toafford5-bromo-3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoro-methyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridineas a solid (4.3 g), which was used without further purification.

Step C-2: Preparation of5-bromo-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine

To a solution of5-bromo-3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine(4.0 g, 9.00 mmol) in dichloromethane (50 ml) at 10° C. was added mCPBA(75 wt % in water) (4.25 g, 18.46 mmol, 75%) in four portions and themixture was stirred at 5° C. for 2 hours, then at room temperatureovernight. The reaction mixture was diluted with tert-butyl methylether, washed successively with a sat. aqueous sodium sodium bisulfitesolution (2×), sat. aqueous sodium hydrogen carbonate (4×) and brine,dried over sodium sulfate and concentrated under reduced pressure. Theresidue was triturated with diethyl ether, the suspension filtered, thesolid washed with cold diethyl ether and dried in vacuo to afford5-bromo-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridineas a solid (3.6 g), mp 173-175° C. LCMS (method 1): 476/478 (M+H)⁺,retention time 1.03 min. ¹H-NMR (CDCl₃, ppm) 1.39 (3H), 3.85 (2H), 4.07(3H), 7.59 (1H), 8.66 (1H), 8.69 (1H), 8.87 (1H), 9.06 (1H).

Step C-3: Preparation of3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-vinyl-pyridine(Compound P12)

Each of two microwave vials were charged with5-bromo-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoro-methyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine(500 mg, 1.050 mmol), dibutoxy(vinyl)borane (0.477 ml, 2.10 mmol) and anaqueous 2M sodium carbonate solution (1.57 ml, 2.0M, 3.14 mmol) inacetonitrile (12 ml). Each mixture was purged with argon for 5 minutes,then chloro(2-dicyclohexylphosphino-2′,4′,6′-triisopropyl-1,1′-biphenyl)[2-(2′-amino-1,1′-biphenyl)]palladium(II)(82 mg, 0.105 mmol) was added, the vials were capped and stirred in themicrowave at 120° C. for 10 minutes. Both reactions were pooled forworkup: after dilution with sat. aqueous sodium hydrogen carbonate, themixture was extracted twice with dichloromethane, the combined organiclayers dried over sodium sulfate and concentrated. The residue waspurified over silica by flash column chromatography (0-70% ethyl acetategradient in cyclohexane) to afford3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-vinyl-pyridine(title compound P12) as a solid (615 mg), mp 67-70° C. LCMS (method 1):424 (M+H)⁺, retention time 0.97 min. ¹H-NMR (CDCl₃, ppm) 1.38 (3H), 3.82(2H), 4.06 (3H), 5.70 (d, 1H), 6.12 (d, 1H), 6.86 (dd, 1H), 7.59 (1H),8.50 (1H), 8.70 (1H), 8.86 (1H), 8.97 (1H).

Example P4: Preparation of5-(6-chloro-2-pyridyl)-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine(Compound P24) Step 1: Preparation of3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine(Compound Z9)

A mixture of5-bromo-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine(1.50 g, 3.15 mmol), potassium acetate (0.805 g, 7.87 mmol) and4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,2-dioxaborolane(1.06 g, 4.09 mmol) in dioxane (10 ml) was purged with argon for 10minutes. 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II) dichloridedichloromethane complex (1:1; PdCl₂(dppf).CH₂Cl₂) (129.9 mg, 0.158 mmol)was then added, and the mixture was stirred in the microwave at 110° C.for 30 minutes. The reaction mixture was diluted with water (50 ml) andextracted with ethyl acetate (5×). The combined organic phases weredried over sodium sulfate and concentrated under reduced pressure. Theresidue was triturated with diethyl ether, the suspension filtered, thesolid washed with cold diethyl ether and dried in vacuo to afford3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridineas a solid (1.12 g), mp 234-236° C. LCMS (method 1): 442 (M+H)⁺,retention time 0.83 min [consistent with the corresponding boronic acidof formula C₁₆H₁₅BF₃N₅O₄S, MW: 441.19]. ¹H-NMR (CDCl₃, ppm) 1.38 (3H),1.40 (12H), 3.79 (2H), 4.05 (3H), 7.58 (1H), 8.70 (1H), 8.86 (2H), 9.27(1H).

Step 2: Preparation of5-(6-chloro-2-pyridyl)-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine(Compound P24)

A mixture of3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine(200 mg, 0.382 mmol), 2-bromo-6-chloro-pyridine (184 mg, 0.955 mmol) andan aqueous 2M sodium carbonate solution (0.573 ml, 2.0M, 1.15 mmol) indioxane (2 ml) was purged with argon for 10 minutes.Tetrakis(triphenylphosphine)palladium(0) (22.3 mg, 0.019 mmol) was thenadded, and the mixture was stirred in the microwave at 85° C. for 40minutes. The reaction mixture was diluted with tert-butyl methyl ether,filtered over diatomaceous earth (Hyflo), the filtrate dried over sodiumsulfate and concentrated to dryness under reduced pressure.

The residue was purified over silica by flash column chromatography(0-30% ethyl acetate gradient in cyclohexane) to afford5-(6-chloro-2-pyridyl)-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine(title compound P24) as a solid (120 mg), mp 172-174° C. LCMS (method1): 509/511 (M+H)⁺, retention time 1.10 min. ¹H-NMR (CDCl₃, ppm) 1.42(3H), 3.89 (2H), 4.10 (3H), 7.46 (1H), 7.59 (1H), 7.84-7.90 (2H), 8.71(1H), 8.87 (1H), 9.05 (1H), 9.63 (1H).

Example P5: Preparation of5-cyclopropyl-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine(Compound P29)

A mixture of5-bromo-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine(250 mg, 0.525 mmol), cyclopropylboronic acid (162 mg, 1.89 mmol) andtripotassium phosphate (689 mg, 3.15 mmol) in toluene/water (2 ml/2 ml)was purged with argon for 10 minutes.Tetrakis(triphenylphosphine)palladium(0) (61.3 mg, 0.053 mmol) was thenadded, and the mixture was stirred in the microwave at 130° C. for atotal of 12 hours. The reaction mixture was concentrated, the residuediluted with tert-butyl methyl ether, the organic phase washed twicewith water, dried over sodium sulfate and evaporated to dryness. Theresidue was purified over silica by flash column chromatography (0-35%ethyl acetate gradient in cyclohexane) to afford5-cyclopropyl-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine(title compound P29) as a solid (90 mg). LCMS (method 2): 438 (M+H)⁺,retention time 1.53 min. ¹H-NMR (CDCl₃, ppm) 0.95 (2H), 1.25 (2H), 1.35(3H), 2.12 (1H), 3.76 (2H), 4.02 (3H), 7.57 (1H), 8.06 (1H), 8.69 (1H),8.76 (1H), 8.85 (1H).

Example P6: Preparation of2-[5-ethylsulfonyl-6-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-3-pyridyl]pyrimidine(Compound P9)

A mixture of3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine(200 mg, 0.382 mmol), 2-bromopyrimidine (151.9 mg, 0.956 mmol) and anaqueous 2M sodium carbonate solution (0.573 ml, 2.0M, 1.15 mmol) indioxane (2 ml) was purged with argon for 10 minutes.Tetrakis(triphenylphosphine)palladium(0) (22.3 mg, 0.019 mmol) was thenadded, and the mixture was stirred in the microwave at 85° C. for 40minutes. The reaction mixture was diluted with water and extracted withethyl acetate (4×), the combined organic phases were washed with waterand brine, dried over sodium sulfate and concentrated under reducedpressure. The residue was purified over silica by flash columnchromatography (cyclohexane/ethyl acetate 3:1) to afford2-[5-ethylsulfonyl-6-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-3-pyridyl]pyrimidine(title compound P9) as a solid (117.6 mg), mp 191-193° C. LCMS (method2): 476 (M+H)⁺, retention time 1.38 min. ¹H-NMR (CDCl₃, ppm) 1.43 (3H),3.87 (2H), 4.11 (3H), 7.39 (1H), 7.59 (1H), 8.72 (1H), 8.87 (1H), 8.93(2H), 9.52 (1H), 10.00 (1H).

Example P7: Preparation of1-[5-ethylsulfonyl-6-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-3-pyridyl]pyrazole-4-carbonitrile(Compound P14) Step 1: Preparation of1-[5-ethylsulfanyl-6-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-3-pyridyl]pyrazole-4-carbonitrile(Compound P30)

To a solution of5-bromo-3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine(300 mg, 0.675 mmol) and 1H-pyrazole-4-carbonitrile (69.15 mg, 0.743mmol) in N,N-dimethylformamide (3.4 ml) under argon was added copper(I)iodide (6.4 mg, 0.034 mmol), N,N′-dimethylethylenediamine (6.0 mg, 7.26μl, 0.068 mmol) and potassium carbonate (18.66 mg, 0.135 mmol). Themixture was stirred at reflux for 4 hours. Same quantities ofN,N′-dimethylethylenediamine, copper(I) iodide and potassium carbonatewere added, and stirring continued at 120° C. overnight. After cooling,the reaction mixture was filtered and concentrated in vacuo. The residuewas purified over silica by flash column chromatography (0-80% ethylacetate gradient in cyclohexane) to afford1-[5-ethylsulfanyl-6-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-3-pyridyl]pyrazole-4-carbonitrile(compound P30) as a solid (125 mg). LCMS (method 1): 457 (M+H)⁺,retention time 1.04 min.

Step 2: Preparation of1-[5-ethylsulfonyl-6-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-3-pyridyl]pyrazole-4-carbonitrile(Title Compound P14)

To a solution of1-[5-ethylsulfanyl-6-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-3-pyridyl]pyrazole-4-carbonitrile(125 mg, 0.274 mmol) in dichloromethane (5 ml) at 0° C. was added mCPBA(70 wt % in water) (162 mg, 0.657 mmol, 70%) in one portion and themixture was stirred at room temperature for 2 hours. The reactionmixture was diluted with dichloromethane, washed successively with a 10%aqueous sodium bisulfite solution (3×), a 1M aqueous sodium hydroxidesolution and brine, dried over magnesium sulfate and concentrated underreduced pressure. The residue was purified over silica by flash columnchromatography (0-20% ethyl acetate gradient in cyclohexane) to afford1-[5-ethylsulfonyl-6-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-3-pyridyl]pyrazole-4-carbonitrile(title compound P14) as a solid. LCMS (method 1): 489 (M+H)⁺, retentiontime 0.97 min. ¹H-NMR (CDCl₃, ppm) 1.42 (3H), 3.93 (2H), 4.11 (3H), 7.62(1H), 8.15 (1H), 8.60 (1H), 8.71 (1H), 8.82 (1H), 8.88 (1H), 9.45 (1H).

Example P8: Preparation of1-[5-ethylsulfonyl-6-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-3-pyridyl]cyclopropanecarbonitrile(Compound P17) Step 1: Preparation of2-[5-ethylsulfonyl-6-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-3-pyridyl]acetonitrile(Compound Z10)

A solution of5-bromo-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine(500 mg, 1.05 mmol) in DMF (2.1 ml) was placed in a 5 ml microwave vial.Under argon, trimethylsilyl acetonitrile (0.24 g, 0.29 ml, 2.1 mmol),difluorozinc (0.066 g, 0.63 mmol), XANTPHOS (0.025 g, 0.042 mmol) andPd₂(dba)₃ (0.020 g, 0.021 mmol) were added, the vial was capped, andheated at 140° C. for one hour in the microwave. LC/MS after this timeshowed reaction completion. The reaction mixture was diluted with ethylacetate, filtered over diatomaceous earth (Hyflo), the filtrate washedwith water and brine. The organic layer was dried over sodium sulfate,filtered and concentrated in vacuo to give the crude product.Purification over a silica gel cartridge (Rf200; 0-75% ethyl acetategradient in cyclohexane) gave the title compound as a beige solid (240mg), mp 216-221° C. LCMS (method 1): 437 (M+H)⁺, retention time 0.88min. ¹H-NMR (CDCl₃, ppm) 1.39 (t, J=7.34 Hz, 3H), 3.86 (q, J=7.34 Hz,2H), 4.02 (s, 2H), 4.08 (s, 3H), 7.60 (m, 1H), 8.51 (d, J=2.20 Hz, 1H),8.70 (s, 1H), 8.87 (d, J=5.13 Hz, 1H), 9.03 (d, J=2.20 Hz, 1H).

Similarly,2-[5-ethylsulfonyl-6-[4-methyl-5-[6-(trifluoromethyl)pyrimidin-4-yl]-1,2,4-triazol-3-yl]-3-pyridyl]acetonitrile(compound Z11, solid, mp 203-204° C.) may be obtained from4-[5-(5-bromo-3-ethylsulfonyl-2-pyridyl)-4-methyl-1,2,4-triazol-3-yl]-6-(trifluoromethyl)pyrimidineand trimethylsilyl acetonitrile according to the protocol describedabove. LCMS (method 1): 438 (M+H)⁺, retention time: 0.85 min. ¹H NMR(CDCl₃, ppm) 1.39 (t, J=7.34 Hz, 3H), 3.81 (q, J=7.34 Hz, 2H), 4.03 (s,2H), 4.12 (s, 3H), 8.51 (d, J=2.20 Hz, 1H), 8.78 (d, J=1.10 Hz, 1H),9.04 (d, J=2.20 Hz, 1H), 9.47 (m, 1H).

Step 2: Preparation of1-[5-ethylsulfonyl-6-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-3-pyridyl]cyclopropanecarbonitrile(Compound P17)

A solution of2-[5-ethylsulfonyl-6-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-3-pyridyl]acetonitrile(0.10 g, 0.23 mmol) in acetonitrile (3 ml) was treated with cesiumcarbonate (0.22 g, 0.69 mmol), and then with 1,2-dibromoethane (0.088 g,0.04 ml, 0.46 mmol). The brown solution was stirred at 80° C. for 6.5hours. The reaction mixture was concentrated in vacuo, and the residuewas dissolved in ethyl acetate and diluted with water. The organic layerwas separated, washed with water and brine, dried over sodium sulfate,filtered and concentrated in vacuo. The crude product was purified overa silica gel cartridge (Rf200; 0-50% ethyl acetate gradient incyclohexane) to give the title product P17 as an off-white solid (50mg), mp 197-198° C. LCMS (method 1): 463 (M+H)⁺, retention time 0.94min. ¹H-NMR (CDCl₃, ppm) 1.37 (t, J=7.34 Hz, 3H), 1.67 (m, 2H), 2.03 (m,2H), 3.85 (q, J=7.34 Hz, 2H), 4.07 (s, 3H), 7.60 (d, J=5.13 Hz, 1H),8.24 (d, J=2.20 Hz, 1H), 8.70 (s, 1H), 8.87 (d, J=5.13 Hz, 1H), 9.07 (d,J=2.20 Hz, 1H).

Example P9: Preparation of3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-6-[4-(trifluoromethyl)phenyl]pyridine(Compound P32) Step A-1: Preparation of methyl6-chloro-3-ethylsulfanyl-pyridine-2-carboxylate

3,6-Dichloro-2-pyridinecarboxylic acid methyl ester (commerciallyavailable, 20.0 g, 97.073 mmol) was dissolved in tetrahydrofuran (200ml) and 18-crown-6-ether (some crystals) was added. Sodiumethanethiolate (9.073 g, 97.073 mmol) was then added in 3 portions atroom temperature and the reaction was stirred for 1 hour at roomtemperature. The reaction mixture was poured on an aqueous saturatedammonium chloride solution (100 ml) and extracted twice with ethylacetate (2×100 ml). The combined organic layers were washed with anaqueous saturated ammonium chloride solution (2×50 ml) and water (3×100ml), dried over sodium sulfate, filtered and evaporated under vacuum.The crude was purified by combi flash chromatography (220 g column;gradient cyclohexane+0-10% ethyl acetate) to give the title compound(14.5 g) as a solid, mp 122-124° C. LCMS (method 1): 232/234 (M+H)⁺,retention time 0.94 min. ¹H NMR (400 MHz, CDCl₃) δ ppm: 1.42 (t, 3H),2.96 (q, 2H), 4.02 (s, 3H), 7.45 (d, 1H), 7.70 (d, 1H).

Step A-2: Preparation of methyl3-ethylsulfanyl-6-[4-(trifluoromethyl)phenyl]pyridine-2-carboxylate

A solution of methyl 6-chloro-3-ethylsulfanyl-pyridine-2-carboxylate(0.3 g, 1.29 mmol) in 1,4-dioxane (7.5 ml) was treated with[4-(trifluoromethyl)phenyl]boronic acid (0.32 g, 1.68 mmol) andanhydrous potassium carbonate (0.537 g, 3.88 mmol), and the mixturepurged with argon for 10 minutes. To this mixture was addedtetrakis(triphenylphosphine)palladium(0) (0.149 g, 0.129 mmol) and thesolution heated at 95° C. overnight. The reaction mixture was quenchedwith water at room temperature and ethyl acetate was added. The aqueouslayer was extracted 3 times with ethyl acetate. The combined organiclayer was washed with an aqueous saturated NaHCO₃ solution and brine,dried over sodium sulfate, filtered and evaporated under vacuum at 45°C. The crude product was dissolved in dichloromethane and adsorbed onTEFLON BULK SORBENTS. The crude was purified by Combi flashchromatography (24 g column; gradient cyclohexane+0-50% ethyl acetate)to give the title compound (280 mg) as a white solid, mp 67-69° C. LCMS(method 1): 342 (M+H)⁺, retention time 1.21 min. ¹H-NMR (CDCl₃, ppm)1.41 (t, J=7.34 Hz, 3H), 2.99 (q, J=7.34 Hz, 2H), 4.03 (s, 3H), 7.72 (d,J=8.07 Hz, 2H), 7.80 (m, 2H), 8.13 (d, J=8.07 Hz, 2H).

Step A-3: Preparation of3-ethylsulfanyl-6-[4-(trifluoromethyl)phenyl]pyridine-2-carbohydrazide

Obtained from methyl3-ethylsulfanyl-6-[4-(trifluoromethyl)phenyl]pyridine-2-carboxylate (500mg, 1.44 mmol) and hydrazine hydrate (0.091 ml, 1.87 mmol) in methanol(10 ml) according to procedure Example P1, step A-5. The mixture wasstirred at reflux temperature for 11 hours. After cooling, thesuspension was diluted with diethyl ether, filtered, the solid washedwith cold diethyl ether and dried in vacuo to afford3-ethylsulfanyl-6-[4-(trifluoromethyl)phenyl]pyridine-2-carbohydrazide(380 mg) as a solid, mp 154-155° C. LCMS (method 1): 342 (M+H)⁺;retention time: 1.02 min. ¹H-NMR (CDCl₃, ppm) 1.45 (t, J=7.34 Hz, 3H),2.98 (q, J=7.34 Hz, 2H), 4.08 (br s, 2H), 7.74 (d, J=8.11 Hz, 2H), 7.79(m, 2H), 8.07 (d, J=8.11 Hz, 2H), 9.00 (br s, 1H).

Step B-1: Preparation of3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-6-[4-(trifluoromethyl)phenyl]pyridine(Compound P31)

Obtained from3-ethylsulfanyl-6-[4-(trifluoromethyl)phenyl]pyridine-2-carbohydrazide(371 mg, 1.09 mmol) and ethylN-methyl-4-(trifluoromethyl)pyridine-2-carboximidothioate (270 mg, 1.09mmol) in pyridine (2 ml) according to procedure Example P3, step C-1.The mixture was heated in the microwave at 180° C. for 40 minutes. Aftercooling, the reaction mixture was concentrated in vacuo. Flashchromatography purification (gradient 0-30% ethyl acetate incyclohexane) afforded3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-6-[4-(trifluoromethyl)phenyl]-pyridine(compound P31) as a solid (260 mg), mp 174-175° C. LCMS (method 1): 510(M+H)⁺; retention time: 1.25 min. ¹H-NMR (CDCl₃, ppm) 1.37 (t, J=7.34Hz, 3H), 3.02 (d, J=7.34 Hz, 2H), 4.22 (s, 3H), 7.59 (dd, J=5.10, 1.10Hz, 1H), 7.73 (d, J=8.07 Hz, 2H), 7.87 (m, 2H), 8.16 (d, J=8.07 Hz, 2H),8.73 (m, 1H), 8.88 (d, J=5.10 Hz, 1H).

Step B-2: Preparation of3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-6-[4-(trifluoromethyl)phenyl]pyridine(Compound P32)

Obtained from3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-6-[4-(trifluoromethyl)phenyl]pyridine(190 mg, 0.373 mmol) and mCPBA (172 mg, 0.750 mmol, 75%) indichloromethane (10 ml) according to procedure Example P1, step C-2. Themixture was stirred at room temperature overnight. Flash chromatographypurification (gradient 0-25% ethyl acetate in cyclohexane) afforded3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-6-[4-(trifluoromethyl)phenyl]pyridine(title compound P32) as a solid (130 mg). LCMS (method 1): 542 (M+H)⁺;retention time: 1.17 min. ¹H-NMR (CDCl₃, ppm) 1.40 (t, J=7.34 Hz, 3H),3.85 (q, J=7.34 Hz, 2H), 4.12 (s, 3H), 7.60 (dd, J=5.10, 1.28 Hz, 1H),7.79 (d, J=8.44 Hz, 2H), 8.13 (d, J=8.44 Hz, 1H), 8.24 (d, J=8.44 Hz,2H), 8.61 (d, J=8.44 Hz, 1H), 8.73 (m, 1H), 8.88 (d, J=5.10 Hz, 1H).

Example P10: Preparation of3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethylsulfanyl)pyridine(Compound P34) Step 1: Preparation of3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethylsulfanyl)pyridine(Compound P33)

A 20 ml microwave vial was charged with a solution of5-bromo-3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine(1.0 g, 2.251 mmol) and (bpy)CuSCF₃ (2.328 g, 7.257 mmol; CAS1413732-47-4) in acetonitrile (15 ml). The mixture was flushed withargon for 10 minutes, the vial was capped, and heated at 100° C. for 20hours. After cooling, the reaction mixture was diluted with t-butylmethyl ether and filtered over diatomaceous earth (Hyflo), the filtratedried over sodium sulfate and concentrated in vacuo. The residue waspurified over silica by flash column chromatography (cyclohexane/ethylacetate, gradient 3:1 to 1:1) to afford3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethylsulfanyl)pyridine(compound P33) as a solid (489 mg), mp 94-95° C. LCMS (method 1): 466(M+H)⁺; retention time: 1.17 min. ¹H-NMR (CDCl₃, ppm) 1.37 (t, J=7.34Hz, 3H), 3.01 (q, J=7.34 Hz, 2H), 4.21 (s, 3H), 7.59 (d, J=5.14 Hz, 1H),7.99 (m, 1H), 8.67 (m, 1H), 8.71 (s, 1H), 8.88 (d, J=5.14 Hz, 1H).

Step 2: Preparation of3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethylsulfanyl)pyridine(Compound P34)

Obtained from3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethylsulfanyl)pyridine(460 mg, 0.988 mmol) and mCPBA (451 mg, 1.987 mmol, 75%) indichloromethane (5 ml) according to procedure Example P1, step C-2. Themixture was stirred at room temperature overnight. Flash chromatographypurification (cyclohexane/ethyl acetate 2:1) afforded3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethylsulfanyl)-pyridine(compound P34) as a solid (420 mg), mp 183-184° C. LCMS (method 1): 498(M+H)⁺; retention time: 1.10 min. ¹H-NMR (CDCl₃, ppm) 1.40 (t, J=7.34Hz, 3H), 3.90 (q, J=7.34 Hz, 2H), 4.12 (s, 3H), 7.61 (d, J=5.14 Hz, 1H),8.70 (s, 1H), 8.79 (d, J=1.83 Hz, 1H), 8.88 (d, J=5.14 Hz, 1H), 9.18 (d,J=1.83 Hz, 1H).

Example P11: Preparation of3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethylsulfonyl)pyridine(Compound P35) and3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethylsulfinyl)pyridine(Compound P36)

To a solution of3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethylsulfanyl)pyridine(200 mg, 0.402 mmol) in dichloromethane (5 ml) at 0° C. was added mCPBA(75 wt % in water) (190 mg, 0.824 mmol, 75%) in one portion and themixture was stirred at 0° C. for 15 minutes, room temperature for 4hours, then at 30° C. for 24 hours. Another portion of mCPBA (18.5 mg,0.080 mmol, 75%) was added and stirring continued at 30° C. for 24hours. The reaction mixture was diluted with dichloromethane, washedsuccessively with a 10% aqueous sodium bisulfite solution (2×), asaturated aqueous sodium bicarbonate solution (4×) and brine, dried oversodium sulfate and concentrated under reduced pressure. The residue waspurified over silica by flash column chromatography (cyclohexane/ethylacetate, gradient 3:1 to 1:1) to afford3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethylsulfonyl)pyridine(compound P35) as a solid (24 mg). LCMS (method 2): 530 (M+H)⁺;retention time: 1.78 min. ¹H-NMR (CDCl₃, ppm) 1.44 (t, J=7.34 Hz, 3H),4.03 (q, J=7.34 Hz, 2H), 4.20 (s, 3H), 7.64 (d, J=5.13 Hz, 1H), 8.71 (s,1H), 8.91 (d, J=5.13 Hz, 1H), 9.11 (d, J=1.91 Hz, 1H), 9.51 (d, J=1.91Hz, 1H).

Further elution then gave3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethylsulfinyl)pyridine(compound P36) as a solid (18 mg). LCMS (method 2): 514 (M+H)⁺;retention time: 1.60 min. ¹H-NMR (CDCl₃, ppm) 1.41 (t, J=7.35 Hz, 3H),3.95 (q, J=7.35 Hz, 2H), 4.15 (s, 3H), 7.63 (d, J=5.14 Hz, 1H), 8.71 (s,1H), 8.91 (m, 2H), 9.32 (d, J=1.83 Hz, 1H).

Example P12: Preparation of4-[5-[6-(3-chloro-1,2,4-triazol-1-yl)-3-ethylsulfonyl-2-pyridyl]-4-methyl-1,2,4-triazol-3-yl]-6-(trifluoromethyl)pyrimidine(Compound P48) Step A-1: Preparation ofN-methyl-6-(trifluoromethyl)pyrimidine-4-carboxamide

To a solution of 6-(trifluoromethyl)pyrimidine-4-carboxylic acid (24.2g, 126.0 mmol) in dichloromethane (300 ml) at 5-10° C. was addeddropwise N,N-dimethylformamide (0.1 ml) and oxalyl chloride (13.6 ml,151.2 mmol). The reaction mixture was stirred at ambient temperatureovernight, then concentrated to dryness in vacuo to afford6-(trifluoromethyl)pyrimidine-4-carbonyl chloride (25.3 g) as a solid.

The title compound N-methyl-6-(trifluoromethyl)pyrimidine-4-carboxamidewas obtained from 6-(tri-fluoromethyl)pyrimidine-4-carbonyl chloride (24g, 114.0 mmol), methylamine (2M in tetrahydrofuran) (142.5 ml, 285.0mmol) and triethylamine (171.0 mmol) in tetrahydrofuran (total 300 ml)according to procedure Example P3, step A-1. The mixture was stirred at0-5° C. for one hour. The crude material obtained after aqueous workupwas used without further purification (19.9 g as a solid). LCMS (method1): 206 (M+H)⁺; retention time: 0.70 min. ¹H-NMR (CDCl₃, ppm) 3.10 (d,3H), 7.97 (br s, 1H), 8.48 (s, 1H), 9.39 (s, 1H).

Step A-2: Preparation ofN-methyl-6-(trifluoromethyl)pyrimidine-4-carbothioamide

Obtained from N-methyl-6-(trifluoromethyl)pyrimidine-4-carboxamide (19.0g, 92.6 mmol) and phosphorus pentasulfide (24.7 g, 55.6 mmol) inpyridine (200 ml) according to procedure Example P3, step A-2. Themixture was stirred at reflux temperature for 4.5 hours. The crudematerial obtained after aqueous workup was used without furtherpurification (16.1 g as a solid), mp 104-106° C. LCMS (method 1): 222(M+H)⁺; retention time: 0.95 min. ¹H-NMR (CDCl₃, ppm) 3.43 (d, 3H), 8.92(s, 1H), 9.33 (s, 1H), 10.06 (br s, 1H).

Step A-3: Preparation of ethylN-methyl-6-(trifluoromethyl)pyrimidine-4-carboximidothioate

Obtained from N-methyl-6-(trifluoromethyl)pyrimidine-4-carbothioamide(15.0 g, 67.8 mmol), sodium ethoxide (21 wt % in EtOH) (67.8 mmol, 25ml) and iodoethane (21.15 g, 135.6 mmol, 11.6 ml) in ethanol (350 ml)according to procedure Example P3, step A-3. The mixture was stirred atroom temperature overnight. The crude material obtained after aqueousworkup was used without further purification (11.8 g as a liquid). LCMS(method 1): 250 (M+H)⁺; retention time: 0.96 min. ¹H-NMR (CDCl₃, ppm)1.19 (t, 3H), 2.97 (q, 2H), 3.56 (s, 3H), 8.04 (s, 1H), 9.42 (s, 1H).

Step B-1: Preparation of6-chloro-3-ethylsulfanyl-pyridine-2-carbohydrazide

Obtained from methyl 6-chloro-3-ethylsulfanyl-pyridine-2-carboxylate(preparation described above, 10.0 g, 43.16 mmol) and hydrazinemonohydrate (4.24 ml, 86.3 mmol) in methanol (100 ml) according toprocedure Example P3, step B-4. The mixture was stirred at reflux for 26hours. The residue obtained after workup was triturated in diethylether, filtered and dried in vacuo to afford6-chloro-3-ethylsulfanyl-pyridine-2-carbohydrazide (6.12 g) as a solid,mp 150-151° C. LCMS (method 1): 232/234 (M+H)⁺; retention time: 0.64min. ¹H-NMR (CDCl₃, ppm) 1.41 (t, 3H), 2.92 (q, 2H), 4.02 (d, 2H), 7.36(d, 1H), 7.62 (d, 1H), 8.76 (br s, 1H).

Step C-1: Preparation of4-[5-(6-chloro-3-ethylsulfanyl-2-pyridyl)-4-methyl-1,2,4-triazol-3-yl]-6-(trifluoromethyl)pyrimidine

Obtained from 6-chloro-3-ethylsulfanyl-pyridine-2-carbohydrazide (4.65g, 20.07 mmol) and ethylN-methyl-6-(trifluoromethyl)pyrimidine-4-carboximidothioate (5.0 g,20.06 mmol) in pyridine (50 ml) according to procedure Example P3, stepC-1. The mixture was heated in the microwave at 160° C. for 60 minutes(four parallel reactions). The crude material obtained after combinedworkup was used without further purification (8.04 g as a solid), mp88-90° C. LCMS (method 1): 401/403 (M+H)⁺; retention time: 1.01 min.¹H-NMR (CDCl₃, ppm) 1.33 (t, 3H), 2.97 (q, 2H), 4.25 (s, 3H), 7.43 (d,1H), 7.77 (d, 1H), 8.79 (s, 1H), 9.46 (s, 1H).

Step C-2: Preparation of4-[5-(6-chloro-3-ethylsulfonyl-2-pyridyl)-4-methyl-1,2,4-triazol-3-yl]-6-(trifluoromethyl)pyrimidine

Obtained from4-[5-(6-chloro-3-ethylsulfanyl-2-pyridyl)-4-methyl-1,2,4-triazol-3-yl]-6-(trifluoromethyl)pyrimidine (2.5 g, 6.24 mmol) and mCPBA (3.2 g, 13.0 mmol, 70%) indichloromethane (30 ml) according to procedure Example P3, step C-2. Themixture was stirred at 0-5° C. for 3 hours. The residue obtained afteraqueous workup was triturated with diethyl ether, the suspensionfiltered and the solid dried in vacuo to afford4-[5-(6-chloro-3-ethylsulfonyl-2-pyridyl)-4-methyl-1,2,4-triazol-3-yl]-6-(trifluoromethyl)pyrimidine(2.2 g) as a solid, mp 183-185° C. LCMS (method 1): 433/435 (M+H)⁺;retention time: 0.94 min. ¹H-NMR (CDCl₃, ppm) 1.37 (t, 3H), 3.76 (q,2H), 4.15 (s, 3H), 7.74 (d, 1H), 8.47 (d, 1H), 8.77 (s, 1H), 9.47 (s,1H).

Step C-3: Preparation of4-[5-[6-(3-chloro-1,2,4-triazol-1-yl)-3-ethylsulfonyl-2-pyridyl]-4-methyl-1,2,4-triazol-3-yl]-6-(trifluoromethyl)pyrimidine(Compound P48)

A solution of4-[5-(6-chloro-3-ethylsulfonyl-2-pyridyl)-4-methyl-1,2,4-triazol-3-yl]-6-(trifluoromethyl)pyrimidine (300 mg, 0.693 mmol) and 3-chloro-1H-1,2,4-triazole (107.6mg, 1.04 mmol) in pyridine (3 ml) under argon was heated in themicrowave at 120° C. for 30 minutes. After cooling, the reaction mixturewas poured onto iced water (20 ml), the suspension filtered and thesolid washed with cold water. This residue was dissolved indichloromethane, dried over sodium sulfate, filtered and concentrated todryness to afford the title compound4-[5-[6-(3-chloro-1,2,4-triazol-1-yl)-3-ethylsulfonyl-2-pyridyl]-4-methyl-1,2,4-triazol-3-yl]-6-(trifluoromethyl)pyrimidine(compound P48) as a solid, mp 261-263° C. LCMS (method 1): 500/502(M+H)⁺; retention time: 0.96 min. ¹H-NMR (CDCl₃, ppm) 1.38 (t, 3H), 3.72(q, 2H), 4.14 (s, 3H), 8.25 (d, 1H), 8.73 (d, 1H), 8.79 (s, 1H), 9.07(s, 1H), 9.48 (s, 1H).

Example P13: Preparation of3-ethylsulfonyl-6-(3-fluorophenyl)-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine(Compound P50)

In a microwave vial, a mixture of6-chloro-3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine(300 mg, 0.695 mmol), (3-fluorophenyl)boronic acid (150 mg, 1.042 mmol)and an aqueous 2M sodium carbonate solution (1.04 ml, 2.0M, 2.08 mmol)in 1,2-dimethoxyethane (3 ml) was purged with argon for 10 minutes.Bis(triphenylphosphine) palladium(II) dichloride (5 mg, 0.007 mmol) wasthen added, and the mixture was stirred in the microwave at 110° C. for30 minutes. The reaction mixture was diluted with ethyl acetate, theorganic phase washed several times with water and brine, dried oversodium sulfate and concentrated under reduced pressure. The residue waspurified over silica by flash column chromatography (ethyl acetategradient in cyclohexane) and the fractions containing product werecombined and concentrated. The residue was triturated with diethylether, the suspension filtered and the solid dried in vacuo to afford3-ethylsulfonyl-6-(3-fluorophenyl)-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]pyridine(compound P50) as a solid (85 mg), mp 182-184° C. LCMS (method 1): 492(M+H)⁺, retention time 1.07 min. 1H-NMR (CDCl3, ppm) 1.40 (t, 3H), 3.86(q, 2H), 4.11 (s, 3H), 7.24 (m, 1H), 7.43 (m, 1H), 7.49-7.62 (m, 3H),8.67 (d, 1H), 8.71 (s, 1H), 8.88 (d, 1H), 9.19 (d, 1H).

TABLE P Examples of compounds of formula (I) LCMS Compound R_(t) [M +H]⁺ No. Structures (min) (measured) Method Mp (° C.) P1

1.97 476/478 2 147-149 P2

1.81 508/510 2 234-235 P3

1.54 432 2 121-123 P4

1.43 464 2 174-176 P5

1.84 500 2 P6

1.71 532 2 172-174 P7

1.59 498/500 2 166-168 P8

1.54 444 2 162-165 P9

1.38 476 2 191-193 P10

2.06 510 2 P11

1.16 542 1 206-208 P12

0.97 424 1 67-70 P13

1.09 468 1 P14

0.97 489 1 P15

0.90 489 1 P16

1.02 489 1 P17

0.94 464 1 197-198 P18

1.10 510/512 1 273-275 P19

1.03 501 1 268-270 P20

1.02 501 1 270-272 P21

1.04 500 1 158-160 P22

1.03 500 1 223-225 P23

0.99 500 1 179-181 P24

1.10 509/511 1 172-174 P25

1.11 509/511 1 229-231 P26

1.09 509/511 1 145-147 P27

0.97 499/501 1 P28

1.04 498/500 1 P29

1.53 438 2 solid P30 1.04 457 1 solid P31 1.25 510 1 174-175 P32

1.17 542 1 solid P33

1.17 466 1 94-95 P34

1.10 498 1 183-184 P35

1.78 530 2 solid P36

1.60 514 2 solid P37

0.89 465 1 133-135 P38

1.01 438 1 179-181 P39

0.89 476 1 145-147 P40 0.85 465 1 207-209 P41 0.97 499/501 1 136-138 P420.96 490 1 229-231 P43 0.94 490 1 235-237 P44 0.94 491 1 205-207 P45

0.94 500/502 1 233-235 P46

0.84 466 1 solid P47

0.85 466 1 245-247 P48

0.96 500/502 1 261-263 P49

0.95 491 1 242-244 P50

1.07 492 1 182-184 P51

1.06 493 1 201-203 P52

1.04 493 1 197-199 P53

1.07 492 1 167-169 P54

0.84 477 1 solid P55 0.98 464 1 solid P56 1.07 498/500 1 251-253 P570.91 464 1 226-228 P58 0.96 439 1 129-131 P59 0.94 477 1 solid

TABLE Z Examples of intermediates of formula (IX), (IX-p), (XVII) and(Iab) LCMS Compound R_(t) [M + H]⁺ No. Structures (min) (measured)Method Mp (° C.) Z1

1.04 444/446 1 122-123 Z2

1.03 476/478 1 173-175 Z3

1.03 445/447 1 108-110 Z4

0.96 477/479 1 solid Z5

solid Z6

150-152 Z7

1.01 401/403 1 88-90 Z8

0.94 433/435 1 183-185 Z9

0.83 442 1 234-236 Z10

0.88 437 1 216-221 Z11

0.85 438 1 203-204

The activity of the compositions according to the invention can bebroadened considerably, and adapted to prevailing circumstances, byadding other insecticidally, acaricidally and/or fungicidally activeingredients. The mixtures of the compounds of formula I with otherinsecticidally, acaricidally and/or fungicidally active ingredients mayalso have further surprising advantages which can also be described, ina wider sense, as synergistic activity. For example, better tolerance byplants, reduced phytotoxicity, insects can be controlled in theirdifferent development stages or better behaviour during theirproduction, for example during grinding or mixing, during their storageor during their use.

Suitable additions to active ingredients here are, for example,representatives of the following classes of active ingredients:organophosphorus compounds, nitrophenol derivatives, thioureas, juvenilehormones, formamidines, benzophenone derivatives, ureas, pyrrolederivatives, carbamates, pyrethroids, chlorinated hydrocarbons,acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoidsand Bacillus thuringiensis preparations.

The following mixtures of the compounds of formula I with activeingredients are preferred (the abbreviation “TX” means “one compoundselected from the group consisting of the compounds described in Tables1 to 12 and Table P of the present invention”):

an adjuvant selected from the group of substances consisting ofpetroleum oils (alternative name) (628)+TX,

an acaricide selected from the group of substances consisting of1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC name) (910)+TX,2,4-dichlorophenyl benzenesulfonate (IUPAC/Chemical Abstracts name)(1059)+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name)(1295)+TX, 4-chlorophenyl phenyl sulfone (IUPAC name) (981)+TX,abamectin (1)+TX, acequinocyl (3)+TX, acetoprole [CCN]+TX, acrinathrin(9)+TX, aldicarb (16)+TX, aldoxycarb (863)+TX, alpha-cypermethrin(202)+TX, amidithion (870)+TX, amidoflumet [CCN]+TX, amidothioate(872)+TX, amiton (875)+TX, amiton hydrogen oxalate (875)+TX, amitraz(24)+TX, aramite (881)+TX, arsenous oxide (882)+TX, AVI 382 (compoundcode)+TX, AZ 60541 (compound code)+TX, azinphos-ethyl (44)+TX,azinphos-methyl (45)+TX, azobenzene (IUPAC name) (888)+TX, azocyclotin(46)+TX, azothoate (889)+TX, benomyl (62)+TX, benoxafos (alternativename) [CCN]+TX, benzoximate (71)+TX, benzyl benzoate (IUPAC name)[CCN]+TX, bifenazate (74)+TX, bifenthrin (76)+TX, binapacryl (907)+TX,brofenvalerate (alternative name)+TX, bromocyclen (918)+TX, bromophos(920)+TX, bromophos-ethyl (921)+TX, bromopropylate (94)+TX, buprofezin(99)+TX, butocarboxim (103)+TX, butoxycarboxim (104)+TX, butylpyridaben(alternative name)+TX, calcium polysulfide (IUPAC name) (111)+TX,camphechlor (941)+TX, carbanolate (943)+TX, carbaryl (115)+TX,carbofuran (118)+TX, carbophenothion (947)+TX, CGA 50′439 (developmentcode) (125)+TX, chinomethionat (126)+TX, chlorbenside (959)+TX,chlordimeform (964)+TX, chlordimeform hydrochloride (964)+TX,chlorfenapyr (130)+TX, chlorfenethol (968)+TX, chlorfenson (970)+TX,chlorfensulfide (971)+TX, chlorfenvinphos (131)+TX, chlorobenzilate(975)+TX, chloromebuform (977)+TX, chloromethiuron (978)+TX,chloropropylate (983)+TX, chlorpyrifos (145)+TX, chlorpyrifos-methyl(146)+TX, chlorthiophos (994)+TX, cinerin I (696)+TX, cinerin II(696)+TX, cinerins (696)+TX, clofentezine (158)+TX, closantel(alternative name) [CCN]+TX, coumaphos (174)+TX, crotamiton (alternativename) [CCN]+TX, crotoxyphos (1010)+TX, cufraneb (1013)+TX, cyanthoate(1020)+TX, cyflumetofen (CAS Reg. No.: 400882-07-7)+TX, cyhalothrin(196)+TX, cyhexatin (199)+TX, cypermethrin (201)+TX, DCPM (1032)+TX, DDT(219)+TX, demephion (1037)+TX, demephion-O (1037)+TX, demephion-S(1037)+TX, demeton (1038)+TX, demeton-methyl (224)+TX, demeton-O(1038)+TX, demeton-O-methyl (224)+TX, demeton-S (1038)+TX,demeton-S-methyl (224)+TX, demeton-S-methylsulfon (1039)+TX,diafenthiuron (226)+TX, dialifos (1042)+TX, diazinon (227)+TX,dichlofluanid (230)+TX, dichlorvos (236)+TX, dicliphos (alternativename)+TX, dicofol (242)+TX, dicrotophos (243)+TX, dienochlor (1071)+TX,dimefox (1081)+TX, dimethoate (262)+TX, dinactin (alternative name)(653)+TX, dinex (1089)+TX, dinex-diclexine (1089)+TX, dinobuton(269)+TX, dinocap (270)+TX, dinocap-4 [CCN]+TX, dinocap-6 [CCN]+TX,dinocton (1090)+TX, dinopenton (1092)+TX, dinosulfon (1097)+TX,dinoterbon (1098)+TX, dioxathion (1102)+TX, diphenyl sulfone (IUPACname) (1103)+TX, disulfiram (alternative name) [CCN]+TX, disulfoton(278)+TX, DNOC (282)+TX, dofenapyn (1113)+TX, doramectin (alternativename) [CCN]+TX, endosulfan (294)+TX, endothion (1121)+TX, EPN (297)+TX,eprinomectin (alternative name) [CCN]+TX, ethion (309)+TX,ethoate-methyl (1134)+TX, etoxazole (320)+TX, etrimfos (1142)+TX,fenazaflor (1147)+TX, fenazaquin (328)+TX, fenbutatin oxide (330)+TX,fenothiocarb (337)+TX, fenpropathrin (342)+TX, fenpyrad (alternativename)+TX, fenpyroximate (345)+TX, fenson (1157)+TX, fentrifanil(1161)+TX, fenvalerate (349)+TX, fipronil (354)+TX, fluacrypyrim(360)+TX, fluazuron (1166)+TX, flubenzimine (1167)+TX, flucycloxuron(366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX, flufenoxuron(370)+TX, flumethrin (372)+TX, fluorbenside (1174)+TX, fluvalinate(1184)+TX, FMC 1137 (development code) (1185)+TX, formetanate (405)+TX,formetanate hydrochloride (405)+TX, formothion (1192)+TX, formparanate(1193)+TX, gamma-HCH (430)+TX, glyodin (1205)+TX, halfenprox (424)+TX,heptenophos (432)+TX, hexadecyl cyclopropanecarboxylate (IUPAC/ChemicalAbstracts name) (1216)+TX, hexythiazox (441)+TX, iodomethane (IUPACname) (542)+TX, isocarbophos (alternative name) (473)+TX, isopropylO-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473)+TX,ivermectin (alternative name) [CCN]+TX, jasmolin I (696)+TX, jasmolin II(696)+TX, jodfenphos (1248)+TX, lindane (430)+TX, lufenuron (490)+TX,malathion (492)+TX, malonoben (1254)+TX, mecarbam (502)+TX, mephosfolan(1261)+TX, mesulfen (alternative name) [CCN]+TX, methacrifos (1266)+TX,methamidophos (527)+TX, methidathion (529)+TX, methiocarb (530)+TX,methomyl (531)+TX, methyl bromide (537)+TX, metolcarb (550)+TX,mevinphos (556)+TX, mexacarbate (1290)+TX, milbemectin (557)+TX,milbemycin oxime (alternative name) [CCN]+TX, mipafox (1293)+TX,monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin (alternativename) [CCN]+TX, naled (567)+TX, NC-184 (compound code)+TX, NC-512(compound code)+TX, nifluridide (1309)+TX, nikkomycins (alternativename) [CCN]+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1 zinc chloridecomplex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250 (compoundcode)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydeprofos (1324)+TX,oxydisulfoton (1325)+TX, pp′-DDT (219)+TX, parathion (615)+TX,permethrin (626)+TX, petroleum oils (alternative name) (628)+TX,phenkapton (1330)+TX, phenthoate (631)+TX, phorate (636)+TX, phosalone(637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosphamidon (639)+TX,phoxim (642)+TX, pirimiphos-methyl (652)+TX, polychloroterpenes(traditional name) (1347)+TX, polynactins (alternative name) (653)+TX,proclonol (1350)+TX, profenofos (662)+TX, promacyl (1354)+TX, propargite(671)+TX, propetamphos (673)+TX, propoxur (678)+TX, prothidathion(1360)+TX, prothoate (1362)+TX, pyrethrin I (696)+TX, pyrethrin II(696)+TX, pyrethrins (696)+TX, pyridaben (699)+TX, pyridaphenthion(701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, quinalphos(711)+TX, quintiofos (1381)+TX, R-1492 (development code) (1382)+TX,RA-17 (development code) (1383)+TX, rotenone (722)+TX, schradan(1389)+TX, sebufos (alternative name)+TX, selamectin (alternative name)[CCN]+TX, SI-0009 (compound code)+TX, sophamide (1402)+TX, spirodiclofen(738)+TX, spiromesifen (739)+TX, SSI-121 (development code) (1404)+TX,sulfiram (alternative name) [CCN]+TX, sulfluramid (750)+TX, sulfotep(753)+TX, sulfur (754)+TX, SZI-121 (development code) (757)+TX,tau-fluvalinate (398)+TX, tebufenpyrad (763)+TX, TEPP (1417)+TX, terbam(alternative name)+TX, tetrachlorvinphos (777)+TX, tetradifon (786)+TX,tetranactin (alternative name) (653)+TX, tetrasul (1425)+TX, thiafenox(alternative name)+TX, thiocarboxime (1431)+TX, thiofanox (800)+TX,thiometon (801)+TX, thioquinox (1436)+TX, thuringiensin (alternativename) [CCN]+TX, triamiphos (1441)+TX, triarathene (1443)+TX, triazophos(820)+TX, triazuron (alternative name)+TX, trichlorfon (824)+TX,trifenofos (1455)+TX, trinactin (alternative name) (653)+TX, vamidothion(847)+TX, vaniliprole [CCN] and YI-5302 (compound code)+TX,

an algicide selected from the group of substances consisting ofbethoxazin [CCN]+TX, copper dioctanoate (IUPAC name) (170)+TX, coppersulfate (172)+TX, cybutryne [CCN]+TX, dichlone (1052)+TX, dichlorophen(232)+TX, endothal (295)+TX, fentin (347)+TX, hydrated lime [CCN]+TX,nabam (566)+TX, quinoclamine (714)+TX, quinonamid (1379)+TX, simazine(730)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltinhydroxide (IUPAC name) (347)+TX,

an anthelmintic selected from the group of substances consisting ofabamectin (1)+TX, crufomate (1011)+TX, doramectin (alternative name)[CCN]+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, eprinomectin(alternative name) [CCN]+TX, ivermectin (alternative name) [CCN]+TX,milbemycin oxime (alternative name) [CCN]+TX, moxidectin (alternativename) [CCN]+TX, piperazine [CCN]+TX, selamectin (alternative name)[CCN]+TX, spinosad (737) and thiophanate (1435)+TX,

an avicide selected from the group of substances consisting ofchloralose (127)+TX, endrin (1122)+TX, fenthion (346)+TX,pyridin-4-amine (IUPAC name) (23) and strychnine (745)+TX, a bactericideselected from the group of substances consisting of1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222)+TX,4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX,8-hydroxyquinoline sulfate (446)+TX, bronopol (97)+TX, copperdioctanoate (IUPAC name) (170)+TX, copper hydroxide (IUPAC name)(169)+TX, cresol [CCN]+TX, dichlorophen (232)+TX, dipyrithione(1105)+TX, dodicin (1112)+TX, fenaminosulf (1144)+TX, formaldehyde(404)+TX, hydrargaphen (alternative name) [CCN]+TX, kasugamycin(483)+TX, kasugamycin hydrochloride hydrate (483)+TX, nickelbis(dimethyldithiocarbamate) (IUPAC name) (1308)+TX, nitrapyrin(580)+TX, octhilinone (590)+TX, oxolinic acid (606)+TX, oxytetracycline(611)+TX, potassium hydroxyquinoline sulfate (446)+TX, probenazole(658)+TX, streptomycin (744)+TX, streptomycin sesquisulfate (744)+TX,tecloftalam (766)+TX, and thiomersal (alternative name) [CCN]+TX,

a biological agent selected from the group of substances consisting ofAdoxophyes orana GV (alternative name) (12)+TX, Agrobacteriumradiobacter (alternative name) (13)+TX, Amblyseius spp. (alternativename) (19)+TX, Anagrapha falcifera NPV (alternative name) (28)+TX,Anagrus atomus (alternative name) (29)+TX, Aphelinus abdominalis(alternative name) (33)+TX, Aphidius colemani (alternative name)(34)+TX, Aphidoletes aphidimyza (alternative name) (35)+TX, Autographacalifornica NPV (alternative name) (38)+TX, Bacillus firmus (alternativename) (48)+TX, Bacillus sphaericus Neide (scientific name) (49)+TX,Bacillus thuringiensis Berliner (scientific name) (51)+TX, Bacillusthuringiensis subsp. aizawai (scientific name) (51)+TX, Bacillusthuringiensis subsp. israelensis (scientific name) (51)+TX, Bacillusthuringiensis subsp. japonensis (scientific name) (51)+TX, Bacillusthuringiensis subsp. kurstaki (scientific name) (51)+TX, Bacillusthuringiensis subsp. tenebrionis (scientific name) (51)+TX, Beauveriabassiana (alternative name) (53)+TX, Beauveria brongniartii (alternativename) (54)+TX, Chrysoperla carnea (alternative name) (151)+TX,Cryptolaemus montrouzieri (alternative name) (178)+TX, Cydia pomonellaGV (alternative name) (191)+TX, Dacnusa sibirica (alternative name)(212)+TX, Diglyphus isaea (alternative name) (254)+TX, Encarsia formosa(scientific name) (293)+TX, Eretmocerus eremicus (alternative name)(300)+TX, Helicoverpa zea NPV (alternative name) (431)+TX,Heterorhabditis bacteriophora and H. megidis (alternative name)(433)+TX, Hippodamia convergens (alternative name) (442)+TX, Leptomastixdactylopii (alternative name) (488)+TX, Macrolophus caliginosus(alternative name) (491)+TX, Mamestra brassicae NPV (alternative name)(494)+TX, Metaphycus helvolus (alternative name) (522)+TX, Metarhiziumanisopliae var. acridum (scientific name) (523)+TX, Metarhiziumanisopliae var. anisopliae (scientific name) (523)+TX, Neodiprionsertifer NPV and N. lecontei NPV (alternative name) (575)+TX, Orius spp.(alternative name) (596)+TX, Paecilomyces fumosoroseus (alternativename) (613)+TX, Phytoseiulus persimilis (alternative name) (644)+TX,Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientificname) (741)+TX, Steinernema bibionis (alternative name) (742)+TX,Steinernema carpocapsae (alternative name) (742)+TX, Steinernema feltiae(alternative name) (742)+TX, Steinernema glaseri (alternative name)(742)+TX, Steinernema riobrave (alternative name) (742)+TX, Steinernemariobravis (alternative name) (742)+TX, Steinernema scapterisci(alternative name) (742)+TX, Steinernema spp. (alternative name)(742)+TX, Trichogramma spp. (alternative name) (826)+TX, Typhlodromusoccidentalis (alternative name) (844) and Verticillium lecanii(alternative name) (848)+TX,

a soil sterilant selected from the group of substances consisting ofiodomethane (IUPAC name) (542) and methyl bromide (537)+TX,

a chemosterilant selected from the group of substances consisting ofapholate [CCN]+TX, bisazir (alternative name) [CCN]+TX, busulfan(alternative name) [CCN]+TX, diflubenzuron (250)+TX, dimatif(alternative name) [CCN]+TX, hemel [CCN]+TX, hempa [CCN]+TX, metepa[CCN]+TX, methiotepa [CCN]+TX, methyl apholate [CCN]+TX, morzid[CCN]+TX, penfluron (alternative name) [CCN]+TX, tepa [CCN]+TX,thiohempa (alternative name) [CCN]+TX, thiotepa (alternative name)[CCN]+TX, tretamine (alternative name) [CCN] and uredepa (alternativename) [CCN]+TX,

an insect pheromone selected from the group of substances consisting of(E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol (IUPAC name) (222)+TX,(E)-tridec-4-en-1-yl acetate (IUPAC name) (829)+TX,(E)-6-methylhept-2-en-4-ol (IUPAC name) (541)+TX,(E,Z)-tetradeca-4,10-dien-1-yl acetate (IUPAC name) (779)+TX,(Z)-dodec-7-en-1-yl acetate (IUPAC name) (285)+TX, (Z)-hexadec-11-enal(IUPAC name) (436)+TX, (Z)-hexadec-11-en-1-yl acetate (IUPAC name)(437)+TX, (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438)+TX,(Z)-icos-13-en-10-one (IUPAC name) (448)+TX, (Z)-tetradec-7-en-1-al(IUPAC name) (782)+TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783)+TX,(Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784)+TX,(7E,9Z)-dodeca-7,9-dien-1-yl acetate (IUPAC name) (283)+TX,(9Z,11E)-tetradeca-9,11-dien-1-yl acetate (IUPAC name) (780)+TX,(9Z,12E)-tetradeca-9,12-dien-1-yl acetate (IUPAC name) (781)+TX,14-methyloctadec-1-ene (IUPAC name) (545)+TX, 4-methylnonan-5-ol with4-methylnonan-5-one (IUPAC name) (544)+TX, alpha-multistriatin(alternative name) [CCN]+TX, brevicomin (alternative name) [CCN]+TX,codlelure (alternative name) [CCN]+TX, codlemone (alternative name)(167)+TX, cuelure (alternative name) (179)+TX, disparlure (277)+TX,dodec-8-en-1-yl acetate (IUPAC name) (286)+TX, dodec-9-en-1-yl acetate(IUPAC name) (287)+TX, dodeca-8+TX, 10-dien-1-yl acetate (IUPAC name)(284)+TX, dominicalure (alternative name) [CCN]+TX, ethyl4-methyloctanoate (IUPAC name) (317)+TX, eugenol (alternative name)[CCN]+TX, frontalin (alternative name) [CCN]+TX, gossyplure (alternativename) (420)+TX, grandlure (421)+TX, grandlure I (alternative name)(421)+TX, grandlure II (alternative name) (421)+TX, grandlure III(alternative name) (421)+TX, grandlure IV (alternative name) (421)+TX,hexalure [CCN]+TX, ipsdienol (alternative name) [CCN]+TX, ipsenol(alternative name) [CCN]+TX, japonilure (alternative name) (481)+TX,lineatin (alternative name) [CCN]+TX, litlure (alternative name)[CCN]+TX, looplure (alternative name) [CCN]+TX, medlure [CCN]+TX,megatomoic acid (alternative name) [CCN]+TX, methyl eugenol (alternativename) (540)+TX, muscalure (563)+TX, octadeca-2,13-dien-1-yl acetate(IUPAC name) (588)+TX, octadeca-3,13-dien-1-yl acetate (IUPAC name)(589)+TX, orfralure (alternative name) [CCN]+TX, oryctalure (alternativename) (317)+TX, ostramone (alternative name) [CCN]+TX, siglure [CCN]+TX,sordidin (alternative name) (736)+TX, sulcatol (alternative name)[CCN]+TX, tetradec-11-en-1-yl acetate (IUPAC name) (785)+TX, trimedlure(839)+TX, trimedlure A (alternative name) (839)+TX, trimedlure B₁(alternative name) (839)+TX, trimedlure B₂ (alternative name) (839)+TX,trimedlure C (alternative name) (839) and trunc-call (alternative name)[CCN]+TX,

an insect repellent selected from the group of substances consisting of2-(octylthio)ethanol (IUPAC name) (591)+TX, butopyronoxyl (933)+TX,butoxy(polypropylene glycol) (936)+TX, dibutyl adipate (IUPAC name)(1046)+TX, dibutyl phthalate (1047)+TX, dibutyl succinate (IUPAC name)(1048)+TX, diethyltoluamide [CCN]+TX, dimethyl carbate [CCN]+TX,dimethyl phthalate [CCN]+TX, ethyl hexanediol (1137)+TX, hexamide[CCN]+TX, methoquin-butyl (1276)+TX, methylneodecanamide [CCN]+TX,oxamate [CCN] and picaridin [CCN]+TX,

an insecticide selected from the group of substances consisting of1-dichloro-1-nitroethane (IUPAC/Chemical Abstracts name) (1058)+TX,1,1-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056), +TX,1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062)+TX,1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063)+TX,1-bromo-2-chloroethane (IUPAC/Chemical Abstracts name) (916)+TX,2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name)(1451)+TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate(IUPAC name) (1066)+TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate(IUPAC/Chemical Abstracts name) (1109)+TX, 2-(2-butoxyethoxy)ethylthiocyanate (IUPAC/Chemical Abstracts name) (935)+TX,2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC/ChemicalAbstracts name) (1084)+TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name)(986)+TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984)+TX,2-imidazolidone (IUPAC name) (1225)+TX, 2-isovalerylindan-1,3-dione(IUPAC name) (1246)+TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate(IUPAC name) (1284)+TX, 2-thiocyanatoethyl laurate (IUPAC name)(1433)+TX, 3-bromo-1-chloroprop-1-ene (IUPAC name) (917)+TX,3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283)+TX,4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate (IUPAC name)(1285)+TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate (IUPACname) (1085)+TX, abamectin (1)+TX, acephate (2)+TX, acetamiprid (4)+TX,acethion (alternative name) [CCN]+TX, acetoprole [CCN]+TX, acrinathrin(9)+TX, acrylonitrile (IUPAC name) (861)+TX, alanycarb (15)+TX, aldicarb(16)+TX, aldoxycarb (863)+TX, aldrin (864)+TX, allethrin (17)+TX,allosamidin (alternative name) [CCN]+TX, allyxycarb (866)+TX,alpha-cypermethrin (202)+TX, alpha-ecdysone (alternative name) [CCN]+TX,aluminium phosphide (640)+TX, amidithion (870)+TX, amidothioate(872)+TX, aminocarb (873)+TX, amiton (875)+TX, amiton hydrogen oxalate(875)+TX, amitraz (24)+TX, anabasine (877)+TX, athidathion (883)+TX, AVI382 (compound code)+TX, AZ 60541 (compound code)+TX, azadirachtin(alternative name) (41)+TX, azamethiphos (42)+TX, azinphos-ethyl(44)+TX, azinphos-methyl (45)+TX, azothoate (889)+TX, Bacillusthuringiensis delta endotoxins (alternative name) (52)+TX, bariumhexafluorosilicate (alternative name) [CCN]+TX, barium polysulfide(IUPAC/Chemical Abstracts name) (892)+TX, barthrin [CCN]+TX, Bayer22/190 (development code) (893)+TX, Bayer 22408 (development code)(894)+TX, bendiocarb (58)+TX, benfuracarb (60)+TX, bensultap (66)+TX,beta-cyfluthrin (194)+TX, beta-cypermethrin (203)+TX, bifenthrin(76)+TX, bioallethrin (78)+TX, bioallethrin S-cyclopentenyl isomer(alternative name) (79)+TX, bioethanomethrin [CCN]+TX, biopermethrin(908)+TX, bioresmethrin (80)+TX, bis(2-chloroethyl) ether (IUPAC name)(909)+TX, bistrifluron (83)+TX, borax (86)+TX, brofenvalerate(alternative name)+TX, bromfenvinfos (914)+TX, bromocyclen (918)+TX,bromo-DDT (alternative name) [CCN]+TX, bromophos (920)+TX,bromophos-ethyl (921)+TX, bufencarb (924)+TX, buprofezin (99)+TX,butacarb (926)+TX, butathiofos (927)+TX, butocarboxim (103)+TX, butonate(932)+TX, butoxycarboxim (104)+TX, butylpyridaben (alternative name)+TX,cadusafos (109)+TX, calcium arsenate [CCN]+TX, calcium cyanide (444)+TX,calcium polysulfide (IUPAC name) (111)+TX, camphechlor (941)+TX,carbanolate (943)+TX, carbaryl (115)+TX, carbofuran (118)+TX, carbondisulfide (IUPAC/Chemical Abstracts name) (945)+TX, carbon tetrachloride(IUPAC name) (946)+TX, carbophenothion (947)+TX, carbosulfan (119)+TX,cartap (123)+TX, cartap hydrochloride (123)+TX, cevadine (alternativename) (725)+TX, chlorbicyclen (960)+TX, chlordane (128)+TX, chlordecone(963)+TX, chlordimeform (964)+TX, chlordimeform hydrochloride (964)+TX,chlorethoxyfos (129)+TX, chlorfenapyr (130)+TX, chlorfenvinphos(131)+TX, chlorfluazuron (132)+TX, chlormephos (136)+TX, chloroform[CCN]+TX, chloropicrin (141)+TX, chlorphoxim (989)+TX, chlorprazophos(990)+TX, chlorpyrifos (145)+TX, chlorpyrifos-methyl (146)+TX,chlorthiophos (994)+TX, chromafenozide (150)+TX, cinerin I (696)+TX,cinerin II (696)+TX, cinerins (696)+TX, cis-resmethrin (alternativename)+TX, cismethrin (80)+TX, clocythrin (alternative name)+TX,cloethocarb (999)+TX, closantel (alternative name) [CCN]+TX,clothianidin (165)+TX, copper acetoarsenite [CCN]+TX, copper arsenate[CCN]+TX, copper oleate [CCN]+TX, coumaphos (174)+TX, coumithoate(1006)+TX, crotamiton (alternative name) [CCN]+TX, crotoxyphos(1010)+TX, crufomate (1011)+TX, cryolite (alternative name) (177)+TX, CS708 (development code) (1012)+TX, cyanofenphos (1019)+TX, cyanophos(184)+TX, cyanthoate (1020)+TX, cyclethrin [CCN]+TX, cycloprothrin(188)+TX, cyfluthrin (193)+TX, cyhalothrin (196)+TX, cypermethrin(201)+TX, cyphenothrin (206)+TX, cyromazine (209)+TX, cythioate(alternative name) [CCN]+TX, d-limonene (alternative name) [CCN]+TX,d-tetramethrin (alternative name) (788)+TX, DAEP (1031)+TX, dazomet(216)+TX, DDT (219)+TX, decarbofuran (1034)+TX, deltamethrin (223)+TX,demephion (1037)+TX, demephion-O (1037)+TX, demephion-S (1037)+TX,demeton (1038)+TX, demeton-methyl (224)+TX, demeton-O (1038)+TX,demeton-O-methyl (224)+TX, demeton-S (1038)+TX, demeton-S-methyl(224)+TX, demeton-S-methylsulphon (1039)+TX, diafenthiuron (226)+TX,dialifos (1042)+TX, diamidafos (1044)+TX, diazinon (227)+TX, dicapthon(1050)+TX, dichlofenthion (1051)+TX, dichlorvos (236)+TX, dicliphos(alternative name)+TX, dicresyl (alternative name) [CCN]+TX, dicrotophos(243)+TX, dicyclanil (244)+TX, dieldrin (1070)+TX, diethyl5-methylpyrazol-3-yl phosphate (IUPAC name) (1076)+TX, diflubenzuron(250)+TX, dilor (alternative name) [CCN]+TX, dimefluthrin [CCN]+TX,dimefox (1081)+TX, dimetan (1085)+TX, dimethoate (262)+TX, dimethrin(1083)+TX, dimethylvinphos (265)+TX, dimetilan (1086)+TX, dinex(1089)+TX, dinex-diclexine (1089)+TX, dinoprop (1093)+TX, dinosam(1094)+TX, dinoseb (1095)+TX, dinotefuran (271)+TX, diofenolan(1099)+TX, dioxabenzofos (1100)+TX, dioxacarb (1101)+TX, dioxathion(1102)+TX, disulfoton (278)+TX, dithicrofos (1108)+TX, DNOC (282)+TX,doramectin (alternative name) [CCN]+TX, DSP (1115)+TX, ecdysterone(alternative name) [CCN]+TX, EI 1642 (development code) (1118)+TX,emamectin (291)+TX, emamectin benzoate (291)+TX, EMPC (1120)+TX,empenthrin (292)+TX, endosulfan (294)+TX, endothion (1121)+TX, endrin(1122)+TX, EPBP (1123)+TX, EPN (297)+TX, epofenonane (1124)+TX,eprinomectin (alternative name) [CCN]+TX, esfenvalerate (302)+TX,etaphos (alternative name) [CCN]+TX, ethiofencarb (308)+TX, ethion(309)+TX, ethiprole (310)+TX, ethoate-methyl (1134)+TX, ethoprophos(312)+TX, ethyl formate (IUPAC name) [CCN]+TX, ethyl-DDD (alternativename) (1056)+TX, ethylene dibromide (316)+TX, ethylene dichloride(chemical name) (1136)+TX, ethylene oxide [CCN]+TX, etofenprox (319)+TX,etrimfos (1142)+TX, EXD (1143)+TX, famphur (323)+TX, fenamiphos(326)+TX, fenazaflor (1147)+TX, fenchlorphos (1148)+TX, fenethacarb(1149)+TX, fenfluthrin (1150)+TX, fenitrothion (335)+TX, fenobucarb(336)+TX, fenoxacrim (1153)+TX, fenoxycarb (340)+TX, fenpirithrin(1155)+TX, fenpropathrin (342)+TX, fenpyrad (alternative name)+TX,fensulfothion (1158)+TX, fenthion (346)+TX, fenthion-ethyl [CCN]+TX,fenvalerate (349)+TX, fipronil (354)+TX, flonicamid (358)+TX,flubendiamide (CAS. Reg. No.: 272451-65-7)+TX, flucofuron (1168)+TX,flucycloxuron (366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX,flufenerim [CCN]+TX, flufenoxuron (370)+TX, flufenprox (1171)+TX,flumethrin (372)+TX, fluvalinate (1184)+TX, FMC 1137 (development code)(1185)+TX, fonofos (1191)+TX, formetanate (405)+TX, formetanatehydrochloride (405)+TX, formothion (1192)+TX, formparanate (1193)+TX,fosmethilan (1194)+TX, fospirate (1195)+TX, fosthiazate (408)+TX,fosthietan (1196)+TX, furathiocarb (412)+TX, furethrin (1200)+TX,gamma-cyhalothrin (197)+TX, gamma-HCH (430)+TX, guazatine (422)+TX,guazatine acetates (422)+TX, GY-81 (development code) (423)+TX,halfenprox (424)+TX, halofenozide (425)+TX, HCH (430)+TX, HEOD(1070)+TX, heptachlor (1211)+TX, heptenophos (432)+TX, heterophos[CCN]+TX, hexaflumuron (439)+TX, HHDN (864)+TX, hydramethylnon (443)+TX,hydrogen cyanide (444)+TX, hydroprene (445)+TX, hyquincarb (1223)+TX,imidacloprid (458)+TX, imiprothrin (460)+TX, indoxacarb (465)+TX,iodomethane (IUPAC name) (542)+TX, IPSP (1229)+TX, isazofos (1231)+TX,isobenzan (1232)+TX, isocarbophos (alternative name) (473)+TX, isodrin(1235)+TX, isofenphos (1236)+TX, isolane (1237)+TX, isoprocarb (472)+TX,isopropyl O-(methoxy-aminothiophosphoryl)salicylate (IUPAC name)(473)+TX, isoprothiolane (474)+TX, isothioate (1244)+TX, isoxathion(480)+TX, ivermectin (alternative name) [CCN]+TX, jasmolin I (696)+TX,jasmolin II (696)+TX, jodfenphos (1248)+TX, juvenile hormone I(alternative name) [CCN]+TX, juvenile hormone II (alternative name)[CCN]+TX, juvenile hormone III (alternative name) [CCN]+TX, kelevan(1249)+TX, kinoprene (484)+TX, lambda-cyhalothrin (198)+TX, leadarsenate [CCN]+TX, lepimectin (CCN)+TX, leptophos (1250)+TX, lindane(430)+TX, lirimfos (1251)+TX, lufenuron (490)+TX, lythidathion(1253)+TX, m-cumenyl methylcarbamate (IUPAC name) (1014)+TX, magnesiumphosphide (IUPAC name) (640)+TX, malathion (492)+TX, malonoben(1254)+TX, mazidox (1255)+TX, mecarbam (502)+TX, mecarphon (1258)+TX,menazon (1260)+TX, mephosfolan (1261)+TX, mercurous chloride (513)+TX,mesulfenfos (1263)+TX, metaflumizone (CCN)+TX, metam (519)+TX,metam-potassium (alternative name) (519)+TX, metam-sodium (519)+TX,methacrifos (1266)+TX, methamidophos (527)+TX, methanesulfonyl fluoride(IUPAC/Chemical Abstracts name) (1268)+TX, methidathion (529)+TX,methiocarb (530)+TX, methocrotophos (1273)+TX, methomyl (531)+TX,methoprene (532)+TX, methoquin-butyl (1276)+TX, methothrin (alternativename) (533)+TX, methoxychlor (534)+TX, methoxyfenozide (535)+TX, methylbromide (537)+TX, methyl isothiocyanate (543)+TX, methylchloroform(alternative name) [CCN]+TX, methylene chloride [CCN]+TX, metofluthrin[CCN]+TX, metolcarb (550)+TX, metoxadiazone (1288)+TX, mevinphos(556)+TX, mexacarbate (1290)+TX, milbemectin (557)+TX, milbemycin oxime(alternative name) [CCN]+TX, mipafox (1293)+TX, mirex (1294)+TX,monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin (alternativename) [CCN]+TX, naftalofos (alternative name) [CCN]+TX, naled (567)+TX,naphthalene (IUPAC/Chemical Abstracts name) (1303)+TX, NC-170(development code) (1306)+TX, NC-184 (compound code)+TX, nicotine(578)+TX, nicotine sulfate (578)+TX, nifluridide (1309)+TX, nitenpyram(579)+TX, nithiazine (1311)+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1zinc chloride complex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250(compound code)+TX, nornicotine (traditional name) (1319)+TX, novaluron(585)+TX, noviflumuron (586)+TX, O-5-dichloro-4-iodophenyl O-ethylethylphosphonothioate (IUPAC name) (1057)+TX, O,O-diethylO-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate (IUPAC name)(1074)+TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-ylphosphorothioate (IUPAC name) (1075)+TX, O,O,O′,O′-tetrapropyldithiopyrophosphate (IUPAC name) (1424)+TX, oleic acid (IUPAC name)(593)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydemeton-methyl(609)+TX, oxydeprofos (1324)+TX, oxydisulfoton (1325)+TX, pp′-DDT(219)+TX, para-dichlorobenzene [CCN]+TX, parathion (615)+TX,parathion-methyl (616)+TX, penfluron (alternative name) [CCN]+TX,pentachlorophenol (623)+TX, pentachlorophenyl laurate (IUPAC name)(623)+TX, permethrin (626)+TX, petroleum oils (alternative name)(628)+TX, PH 60-38 (development code) (1328)+TX, phenkapton (1330)+TX,phenothrin (630)+TX, phenthoate (631)+TX, phorate (636)+TX, phosalone(637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosnichlor (1339)+TX,phosphamidon (639)+TX, phosphine (IUPAC name) (640)+TX, phoxim (642)+TX,phoxim-methyl (1340)+TX, pirimetaphos (1344)+TX, pirimicarb (651)+TX,pirimiphos-ethyl (1345)+TX, pirimiphos-methyl (652)+TX,polychlorodicyclopentadiene isomers (IUPAC name) (1346)+TX,polychloroterpenes (traditional name) (1347)+TX, potassium arsenite[CCN]+TX, potassium thiocyanate [CCN]+TX, prallethrin (655)+TX,precocene I (alternative name) [CCN]+TX, precocene II (alternative name)[CCN]+TX, precocene III (alternative name) [CCN]+TX, primidophos(1349)+TX, profenofos (662)+TX, profluthrin [CCN]+TX, promacyl(1354)+TX, promecarb (1355)+TX, propaphos (1356)+TX, propetamphos(673)+TX, propoxur (678)+TX, prothidathion (1360)+TX, prothiofos(686)+TX, prothoate (1362)+TX, protrifenbute [CCN]+TX, pymetrozine(688)+TX, pyraclofos (689)+TX, pyrazophos (693)+TX, pyresmethrin(1367)+TX, pyrethrin I (696)+TX, pyrethrin II (696)+TX, pyrethrins(696)+TX, pyridaben (699)+TX, pyridalyl (700)+TX, pyridaphenthion(701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, pyriproxyfen(708)+TX, quassia (alternative name) [CCN]+TX, quinalphos (711)+TX,quinalphos-methyl (1376)+TX, quinothion (1380)+TX, quintiofos (1381)+TX,R-1492 (development code) (1382)+TX, rafoxanide (alternative name)[CCN]+TX, resmethrin (719)+TX, rotenone (722)+TX, RU 15525 (developmentcode) (723)+TX, RU 25475 (development code) (1386)+TX, ryania(alternative name) (1387)+TX, ryanodine (traditional name) (1387)+TX,sabadilla (alternative name) (725)+TX, schradan (1389)+TX, sebufos(alternative name)+TX, selamectin (alternative name) [CCN]+TX, SI-0009(compound code)+TX, SI-0205 (compound code)+TX, SI-0404 (compoundcode)+TX, SI-0405 (compound code)+TX, silafluofen (728)+TX, SN 72129(development code) (1397)+TX, sodium arsenite [CCN]+TX, sodium cyanide(444)+TX, sodium fluoride (IUPAC/Chemical Abstracts name) (1399)+TX,sodium hexafluorosilicate (1400)+TX, sodium pentachlorophenoxide(623)+TX, sodium selenate (IUPAC name) (1401)+TX, sodium thiocyanate[CCN]+TX, sophamide (1402)+TX, spinosad (737)+TX, spiromesifen (739)+TX,spirotetrmat (CCN)+TX, sulcofuron (746)+TX, sulcofuron-sodium (746)+TX,sulfluramid (750)+TX, sulfotep (753)+TX, sulfuryl fluoride (756)+TX,sulprofos (1408)+TX, tar oils (alternative name) (758)+TX,tau-fluvalinate (398)+TX, tazimcarb (1412)+TX, TDE (1414)+TX,tebufenozide (762)+TX, tebufenpyrad (763)+TX, tebupirimfos (764)+TX,teflubenzuron (768)+TX, tefluthrin (769)+TX, temephos (770)+TX, TEPP(1417)+TX, terallethrin (1418)+TX, terbam (alternative name)+TX,terbufos (773)+TX, tetrachloroethane [CCN]+TX, tetrachlorvinphos(777)+TX, tetramethrin (787)+TX, theta-cypermethrin (204)+TX,thiacloprid (791)+TX, thiafenox (alternative name)+TX, thiamethoxam(792)+TX, thicrofos (1428)+TX, thiocarboxime (1431)+TX, thiocyclam(798)+TX, thiocyclam hydrogen oxalate (798)+TX, thiodicarb (799)+TX,thiofanox (800)+TX, thiometon (801)+TX, thionazin (1434)+TX, thiosultap(803)+TX, thiosultap-sodium (803)+TX, thuringiensin (alternative name)[CCN]+TX, tolfenpyrad (809)+TX, tralomethrin (812)+TX, transfluthrin(813)+TX, transpermethrin (1440)+TX, triamiphos (1441)+TX, triazamate(818)+TX, triazophos (820)+TX, triazuron (alternative name)+TX,trichlorfon (824)+TX, trichlormetaphos-3 (alternative name) [CCN]+TX,trichloronat (1452)+TX, trifenofos (1455)+TX, triflumuron (835)+TX,trimethacarb (840)+TX, triprene (1459)+TX, vamidothion (847)+TX,vaniliprole [CCN]+TX, veratridine (alternative name) (725)+TX, veratrine(alternative name) (725)+TX, XMC (853)+TX, xylylcarb (854)+TX, YI-5302(compound code)+TX, zeta-cypermethrin (205)+TX, zetamethrin (alternativename)+TX, zinc phosphide (640)+TX, zolaprofos (1469) and ZXI 8901(development code) (858)+TX, cyantraniliprole [736994-63-19+TX,chlorantraniliprole [500008-45-7]+TX, cyenopyrafen [560121-52-0]+TX,cyflumetofen [400882-07-7]+TX, pyrifluquinazon [337458-27-2]+TX,spinetoram [187166-40-1+187166-15-0]+TX, spirotetramat [203313-25-1]+TX,sulfoxaflor [946578-00-3]+TX, flufiprole [704886-18-0]+TX, meperfluthrin[915288-13-0]+TX, tetramethylfluthrin [84937-88-2]+TX, triflumezopyrim(disclosed in WO 2012/092115)+TX, fluxametamide (WO 2007/026965)+TX,epsilon-metofluthrin [240494-71-7]+TX, epsilon-momfluorothrin[1065124-65-3]+TX, fluazaindolizine [1254304-22-7]+TX, chloroprallethrin[399572-87-3]+TX, fluxametamide [928783-29-3]+TX, cyhalodiamide[1262605-53-7]+TX, tioxazafen [330459-31-9]+TX, broflanilide[1207727-04-5]+TX, flufiprole [704886-18-0]+TX, cyclaniliprole[1031756-98-5]+TX, tetraniliprole [1229654-66-3]+TX, guadipyr (describedin WO2010/060231)+TX, cycloxaprid (described in WO2005/077934)+TX,

a molluscicide selected from the group of substances consisting ofbis(tributyltin) oxide (IUPAC name) (913)+TX, bromoacetamide [CCN]+TX,calcium arsenate [CCN]+TX, cloethocarb (999)+TX, copper acetoarsenite[CCN]+TX, copper sulfate (172)+TX, fentin (347)+TX, ferric phosphate(IUPAC name) (352)+TX, metaldehyde (518)+TX, methiocarb (530)+TX,niclosamide (576)+TX, niclosamide-olamine (576)+TX, pentachlorophenol(623)+TX, sodium pentachlorophenoxide (623)+TX, tazimcarb (1412)+TX,thiodicarb (799)+TX, tributyltin oxide (913)+TX, trifenmorph (1454)+TX,trimethacarb (840)+TX, triphenyltin acetate (IUPAC name) (347) andtriphenyltin hydroxide (IUPAC name) (347)+TX, pyriprole[394730-71-3]+TX,

a nematicide selected from the group of substances consisting ofAKD-3088 (compound code)+TX, 1,2-dibromo-3-chloropropane (IUPAC/ChemicalAbstracts name) (1045)+TX, 1,2-dichloropropane (IUPAC/Chemical Abstractsname) (1062)+TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPACname) (1063)+TX, 1,3-dichloropropene (233)+TX,3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC/Chemical Abstractsname) (1065)+TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name)(980)+TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid (IUPACname) (1286)+TX, 6-isopentenylaminopurine (alternative name) (210)+TX,abamectin (1)+TX, acetoprole [CCN]+TX, alanycarb (15)+TX, aldicarb(16)+TX, aldoxycarb (863)+TX, AZ 60541 (compound code)+TX, benclothiaz[CCN]+TX, benomyl (62)+TX, butylpyridaben (alternative name)+TX,cadusafos (109)+TX, carbofuran (118)+TX, carbon disulfide (945)+TX,carbosulfan (119)+TX, chloropicrin (141)+TX, chlorpyrifos (145)+TX,cloethocarb (999)+TX, cytokinins (alternative name) (210)+TX, dazomet(216)+TX, DBCP (1045)+TX, DCIP (218)+TX, diamidafos (1044)+TX,dichlofenthion (1051)+TX, dicliphos (alternative name)+TX, dimethoate(262)+TX, doramectin (alternative name) [CCN]+TX, emamectin (291)+TX,emamectin benzoate (291)+TX, eprinomectin (alternative name) [CCN]+TX,ethoprophos (312)+TX, ethylene dibromide (316)+TX, fenamiphos (326)+TX,fenpyrad (alternative name)+TX, fensulfothion (1158)+TX, fosthiazate(408)+TX, fosthietan (1196)+TX, furfural (alternative name) [CCN]+TX,GY-81 (development code) (423)+TX, heterophos [CCN]+TX, iodomethane(IUPAC name) (542)+TX, isamidofos (1230)+TX, isazofos (1231)+TX,ivermectin (alternative name) [CCN]+TX, kinetin (alternative name)(210)+TX, mecarphon (1258)+TX, metam (519)+TX, metam-potassium(alternative name) (519)+TX, metam-sodium (519)+TX, methyl bromide(537)+TX, methyl isothiocyanate (543)+TX, milbemycin oxime (alternativename) [CCN]+TX, moxidectin (alternative name) [CCN]+TX, Myrotheciumverrucaria composition (alternative name) (565)+TX, NC-184 (compoundcode)+TX, oxamyl (602)+TX, phorate (636)+TX, phosphamidon (639)+TX,phosphocarb [CCN]+TX, sebufos (alternative name)+TX, selamectin(alternative name) [CCN]+TX, spinosad (737)+TX, terbam (alternativename)+TX, terbufos (773)+TX, tetrachlorothiophene (IUPAC/ChemicalAbstracts name) (1422)+TX, thiafenox (alternative name)+TX, thionazin(1434)+TX, triazophos (820)+TX, triazuron (alternative name)+TX,xylenols [CCN]+TX, YI-5302 (compound code) and zeatin (alternative name)(210)+TX, fluensulfone [318290-98-1]+TX,

a nitrification inhibitor selected from the group of substancesconsisting of potassium ethylxanthate [CCN] and nitrapyrin (580)+TX,

a plant activator selected from the group of substances consisting ofacibenzolar (6)+TX, acibenzolar-S-methyl (6)+TX, probenazole (658) andReynoutria sachalinensis extract (alternative name) (720)+TX,

a rodenticide selected from the group of substances consisting of2-isovalerylindan-1,3-dione (IUPAC name) (1246)+TX,4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX,alpha-chlorohydrin [CCN]+TX, aluminium phosphide (640)+TX, antu(880)+TX, arsenous oxide (882)+TX, barium carbonate (891)+TX,bisthiosemi (912)+TX, brodifacoum (89)+TX, bromadiolone (91)+TX,bromethalin (92)+TX, calcium cyanide (444)+TX, chloralose (127)+TX,chlorophacinone (140)+TX, cholecalciferol (alternative name) (850)+TX,coumachlor (1004)+TX, coumafuryl (1005)+TX, coumatetralyl (175)+TX,crimidine (1009)+TX, difenacoum (246)+TX, difethialone (249)+TX,diphacinone (273)+TX, ergocalciferol (301)+TX, flocoumafen (357)+TX,fluoroacetamide (379)+TX, flupropadine (1183)+TX, flupropadinehydrochloride (1183)+TX, gamma-HCH (430)+TX, HCH (430)+TX, hydrogencyanide (444)+TX, iodomethane (IUPAC name) (542)+TX, lindane (430)+TX,magnesium phosphide (IUPAC name) (640)+TX, methyl bromide (537)+TX,norbormide (1318)+TX, phosacetim (1336)+TX, phosphine (IUPAC name)(640)+TX, phosphorus [CCN]+TX, pindone (1341)+TX, potassium arsenite[CCN]+TX, pyrinuron (1371)+TX, scilliroside (1390)+TX, sodium arsenite[CCN]+TX, sodium cyanide (444)+TX, sodium fluoroacetate (735)+TX,strychnine (745)+TX, thallium sulfate [CCN]+TX, warfarin (851) and zincphosphide (640)+TX,

a synergist selected from the group of substances consisting of2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934)+TX,5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903)+TX,farnesol with nerolidol (alternative name) (324)+TX, MB-599 (developmentcode) (498)+TX, MGK 264 (development code) (296)+TX, piperonyl butoxide(649)+TX, piprotal (1343)+TX, propyl isomer (1358)+TX, S421 (developmentcode) (724)+TX, sesamex (1393)+TX, sesasmolin (1394) and sulfoxide(1406)+TX,

an animal repellent selected from the group of substances consisting ofanthraquinone (32)+TX, chloralose (127)+TX, copper naphthenate [CCN]+TX,copper oxychloride (171)+TX, diazinon (227)+TX, dicyclopentadiene(chemical name) (1069)+TX, guazatine (422)+TX, guazatine acetates(422)+TX, methiocarb (530)+TX, pyridin-4-amine (IUPAC name) (23)+TX,thiram (804)+TX, trimethacarb (840)+TX, zinc naphthenate [CCN] and ziram(856)+TX,

a virucide selected from the group of substances consisting of imanin(alternative name) [CCN] and ribavirin (alternative name) [CCN]+TX,

a wound protectant selected from the group of substances consisting ofmercuric oxide (512)+TX, octhilinone (590) and thiophanate-methyl(802)+TX,

and biologically active compounds selected from the group consisting ofazaconazole (60207-31-0]+TX, bitertanol [70585-36-3]+TX, bromuconazole[116255-48-2]+TX, cyproconazole [94361-06-5]+TX, difenoconazole[119446-68-3]+TX, diniconazole [83657-24-3]+TX, epoxiconazole[106325-08-0]+TX, fenbuconazole [114369-43-6]+TX, fluquinconazole[136426-54-5]+TX, flusilazole [85509-19-9]+TX, flutriafol[76674-21-0]+TX, hexaconazole [79983-71-4]+TX, imazalil [35554-44-0]+TX,imibenconazole [86598-92-7]+TX, ipconazole [125225-28-7]+TX, metconazole[125116-23-6]+TX, myclobutanil [88671-89-0]+TX, pefurazoate[101903-30-4]+TX, penconazole [66246-88-6]+TX, prothioconazole[178928-70-6]+TX, pyrifenox [88283-41-4]+TX, prochloraz [67747-09-5]+TX,propiconazole [60207-90-1]+TX, simeconazole [149508-90-7]+TX,tebuconazole [107534-96-3]+TX, tetraconazole [112281-77-3]+TX,triadimefon [43121-43-3]+TX, triadimenol [55219-65-3]+TX, triflumizole[99387-89-0]+TX, triticonazole [131983-72-7]+TX, ancymidol[12771-68-5]+TX, fenarimol [60168-88-9]+TX, nuarimol [63284-71-9]+TX,bupirimate [41483-43-6]+TX, dimethirimol [5221-53-4]+TX, ethirimol[23947-60-6]+TX, dodemorph [1593-77-7]+TX, fenpropidine [67306-00-7]+TX,fenpropimorph [67564-91-4]+TX, spiroxamine [118134-30-8]+TX, tridemorph[81412-43-3]+TX, cyprodinil [121552-61-2]+TX, mepanipyrim[110235-47-7]+TX, pyrimethanil [53112-28-0]+TX, fenpiclonil[74738-17-3]+TX, fludioxonil [131341-86-1]+TX, benalaxyl[71626-11-4]+TX, furalaxyl [57646-30-7]+TX, metalaxyl [57837-19-1]+TX,R-metalaxyl [70630-17-0]+TX, ofurace [58810-48-3]+TX, oxadixyl[77732-09-3]+TX, benomyl [17804-35-2]+TX, carbendazim [10605-21-7]+TX,debacarb [62732-91-6]+TX, fuberidazole [3878-19-1]+TX, thiabendazole[148-79-8]+TX, chlozolinate [84332-86-5]+TX, dichlozoline[24201-58-9]+TX, iprodione [36734-19-7]+TX, myclozoline [54864-61-8]+TX,procymidone [32809-16-8]+TX, vinclozoline [50471-44-8]+TX, boscalid[188425-85-6]+TX, carboxin [5234-68-4]+TX, fenfuram [24691-80-3]+TX,flutolanil [66332-96-5]+TX, mepronil [55814-41-0]+TX, oxycarboxin[5259-88-1]+TX, penthiopyrad [183675-82-3]+TX, thifluzamide[130000-40-7]+TX, guazatine [108173-90-6]+TX, dodine [2439-10-3][112-65-2] (free base)+TX, iminoctadine [13516-27-3]+TX, azoxystrobin[131860-33-8]+TX, dimoxystrobin [149961-52-4]+TX, enestroburin {Proc.BCPC, Int. Congr., Glasgow, 2003, 1, 93}+TX, fluoxastrobin[361377-29-9]+TX, kresoxim-methyl [143390-89-0]+TX, metominostrobin[133408-50-1]+TX, trifloxystrobin [141517-21-7]+TX, orysastrobin[248593-16-0]+TX, picoxystrobin [117428-22-5]+TX, pyraclostrobin[175013-18-0]+TX, ferbam [14484-64-1]+TX, mancozeb [8018-01-7]+TX, maneb[12427-38-2]+TX, metiram [9006-42-2]+TX, propineb [12071-83-9]+TX,thiram [137-26-8]+TX, zineb [12122-67-7]+TX, ziram [137-30-4]+TX,captafol [2425-06-1]+TX, captan [133-06-2]+TX, dichlofluanid[1085-98-9]+TX, fluoroimide [41205-21-4]+TX, folpet [133-07-3]+TX,tolylfluanid [731-27-1]+TX, bordeaux mixture [8011-63-0]+TX,copperhydroxid [20427-59-2]+TX, copperoxychlorid [1332-40-7]+TX,coppersulfat [7758-98-7]+TX, copperoxid [1317-39-1]+TX, mancopper[53988-93-5]+TX, oxine-copper [10380-28-6]+TX, dinocap [131-72-6]+TX,nitrothal-isopropyl [10552-74-6]+TX, edifenphos [17109-49-8]+TX,iprobenphos [26087-47-8]+TX, isoprothiolane [50512-35-1]+TX, phosdiphen[36519-00-3]+TX, pyrazophos [13457-18-6]+TX, tolclofos-methyl[57018-04-9]+TX, acibenzo-lar-S-methyl [135158-54-2]+TX, anilazine[101-05-3]+TX, benthiavalicarb [413615-35-7]+TX, blasticidin-S[2079-00-7]+TX, chinomethionat [2439-01-2]+TX, chloroneb [2675-77-6]+TX,chlorothalonil [1897-45-6]+TX, cyflufenamid [180409-60-3]+TX, cymoxanil[57966-95-7]+TX, dichlone [117-80-6]+TX, diclocymet [139920-32-4]+TX,diclomezine [62865-36-5]+TX, dicloran [99-30-9]+TX, diethofencarb[87130-20-9]+TX, dimethomorph [110488-70-5]+TX, SYP-L190 (Flumorph)[211867-47-9]+TX, dithianon [3347-22-6]+TX, ethaboxam [162650-77-3]+TX,etridiazole [2593-15-9]+TX, famoxadone [131807-57-3]+TX, fenamidone[161326-34-7]+TX, fenoxanil [115852-48-7]+TX, fentin [668-34-8]+TX,ferimzone [89269-64-7]+TX, fluazinam [79622-59-6]+TX, fluopicolide[239110-15-7]+TX, flusulfamide [106917-52-6]+TX, fenhexamid[126833-17-8]+TX, fosetyl-aluminium [39148-24-8]+TX, hymexazol[10004-44-1]+TX, iprovalicarb [140923-17-7]+TX, IKF-916 (Cyazofamid)[120116-88-3]+TX, kasugamycin [6980-18-3]+TX, methasulfocarb[66952-49-6]+TX, metrafenone [220899-03-6]+TX, pencycuron[66063-05-6]+TX, phthalide [27355-22-2]+TX, polyoxins [11113-80-7]+TX,probenazole [27605-76-1]+TX, propamocarb [25606-41-1]+TX, proquinazid[189278-12-4]+TX, pyroquilon [57369-32-1]+TX, quinoxyfen[124495-18-7]+TX, quintozene [82-68-8]+TX, sulfur [7704-34-9]+TX,tiadinil [223580-51-6]+TX, triazoxide [72459-58-6]+TX, tricyclazole[41814-78-2]+TX, triforine [26644-46-2]+TX, validamycin [37248-47-8]+TX,zoxamide (RH7281) [156052-68-5]+TX, mandipropamid [374726-62-2]+TX,isopyrazam [881685-58-1]+TX, sedaxane [874967-67-6]+TX,3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide(disclosed in WO 2007/048556)+TX,3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(3′,4′,5′-trifluoro-biphenyl-2-yl)-amide (disclosed in WO2006/087343)+TX,[(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11Hnaphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methyl-cyclopropanecarboxylate[915972-17-7]+TX,1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide[926914-55-8]+TX; lancotrione [1486617-21-3], florpyrauxifen[943832-81-3], ipfentrifluconazole[1417782-08-1], mefentrifluconazole[1417782-03-6], quinofumelin [861647-84-9], chloroprallethrin[399572-87-3], cyhalodiamide [1262605-53-7], fluazaindolizine[1254304-22-7], fluxametamide [928783-29-3], epsilon-metofluthrin[240494-71-7], epsilon-momfluorothrin [1065124-65-3], pydiflumetofen[1228284-64-7], kappa-bifenthrin [439680-76-9], broflanilide[1207727-04-5], dicloromezotiaz [1263629-39-5], dipymetitrone[16114-35-5], pyraziflumid [942515-63-1] and kappa-tefluthrin[391634-71-2]; and

microbials including: Acinetobacter lwoffii+TX, Acremoniumalternatum+TX+TX, Acremonium cephalosporium+TX+TX, Acremoniumdiospyri+TX, Acremonium obclavatum+TX, Adoxophyes orana granulovirus(AdoxGV) (Capex®)+TX, Agrobacterium radiobacter strain K84(Galltrol-A®)+TX, Alternaria alternate+TX, Alternaria cassia+TX,Alternaria destruens (Smolder®)+TX, Ampelomyces quisqualis (AQ10®)+TX,Aspergillus flavus AF36 (AF36®)+TX, Aspergillus flavus NRRL 21882(Aflaguard®)+TX, Aspergillus spp.+TX, Aureobasidium pullulans+TX,Azospirillum+TX, (MicroAZ®+TX, TAZO B®)+TX, Azotobacter+TX, Azotobacterchroocuccum (Azotomeal®)+TX, Azotobacter cysts (Bionatural BloomingBlossoms®)+TX, Bacillus amyloliquefaciens+TX, Bacillus cereus+TX,Bacillus chitinosporus strain CM-1+TX, Bacillus chitinosporus strainAQ746+TX, Bacillus licheniformis strain HB-2 (Biostart™ Rhizoboost®)+TX,Bacillus licheniformis strain 3086 (EcoGuard®+TX, Green Releaf®)+TX,Bacillus circulans+TX, Bacillus firmus (BioSafe®+TX, BioNem-WP®+TX,VOTiVO®)+TX, Bacillus firmus strain I-1582+TX, Bacillus macerans+TX,Bacillus marismortui+TX, Bacillus megaterium+TX, Bacillus mycoidesstrain AQ726+TX, Bacillus papillae (Milky Spore Powder®)+TX, Bacilluspumilus spp.+TX, Bacillus pumilus strain GB34 (Yield Shield®)+TX,Bacillus pumilus strain AQ717+TX, Bacillus pumilus strain QST 2808(Sonata®+TX, Ballad Plus®)+TX, Bacillus spahericus (VectoLex®)+TX,Bacillus spp.+TX, Bacillus spp. strain AQ175+TX, Bacillus spp. strainAQ177+TX, Bacillus spp. strain AQ178+TX, Bacillus subtilis strain QST713 (CEASE®+TX, Serenade®+TX, Rhapsody®)+TX, Bacillus subtilis strainQST 714 (JAZZ®)+TX, Bacillus subtilis strain AQ153+TX, Bacillus subtilisstrain AQ743+TX, Bacillus subtilis strain QST3002+TX, Bacillus subtilisstrain QST3004+TX, Bacillus subtilis var. amyloliquefaciens strain FZB24(Taegro®+TX, Rhizopro®)+TX, Bacillus thuringiensis Cry 2Ae+TX, Bacillusthuringiensis Cry1Ab+TX, Bacillus thuringiensis aizawai GC 91(Agree®)+TX, Bacillus thuringiensis israelensis (BMP123®+TX,Aquabac®+TX, VectoBac®)+TX, Bacillus thuringiensis kurstaki(Javelin®+TX, Deliver®+TX, CryMax®+TX, Bonide®+TX, Scutella WP®+TX,Turilav WP®+TX, Astuto®+TX, Dipel WP®+TX, Biobit®+TX, Foray®)+TX,Bacillus thuringiensis kurstaki BMP 123 (Baritone®)+TX, Bacillusthuringiensis kurstaki HD-1 (Bioprotec-CAF/3P®)+TX, Bacillusthuringiensis strain BD#32+TX, Bacillus thuringiensis strain AQ52+TX,Bacillus thuringiensis var. aizawai (XenTari®+TX, DiPel®)+TX, bacteriaspp. (GROWMEND®+TX, GROWSWEET®+TX, Shootup®)+TX, bacteriophage ofClavipacter michiganensis (AgriPhage®)+TX, Bakflor®+TX, Beauveriabassiana (Beaugenic®+TX, Brocaril WP®)+TX, Beauveria bassiana GHA(Mycotrol ES®+TX, Mycotrol O®+TX, BotaniGuard®)+TX, Beauveriabrongniartii (Engerlingspilz®+TX, Schweizer Beauveria®+TX,Melocont®)+TX, Beauveria spp.+TX, Botrytis cineria+TX, Bradyrhizobiumjaponicum (TerraMax®)+TX, Brevibacillus brevis+TX, Bacillusthuringiensis tenebrionis (Novodor®)+TX, BtBooster+TX, Burkholderiacepacia (Deny®+TX, Intercept®+TX, Blue Circle®)+TX, Burkholderiagladii+TX, Burkholderia gladioli+TX, Burkholderia spp.+TX, Canadianthistle fungus (CBH Canadian Bioherbicide®)+TX, Candida butyri+TX,Candida famata+TX, Candida fructus+TX, Candida glabrata+TX, Candidaguiffiermondii+TX, Candida melibiosica+TX, Candida oleophila strainO+TX, Candida parapsilosis+TX, Candida pelliculosa+TX, Candidapulcherrima+TX, Candida reukaufii+TX, Candida saitoana (Bio-Coat®+TX,Biocure®)+TX, Candida sake+TX, Candida spp.+TX, Candida tenius+TX,Cedecea dravisae+TX, Cellulomonas flavigena+TX, Chaetomium cochliodes(Nova-Cide®)+TX, Chaetomium globosum (Nova-Cide®)+TX, Chromobacteriumsubtsugae strain PRAA4-1T (Grandevo®)+TX, Cladosporiumcladosporioides+TX, Cladosporium oxysporum+TX, Cladosporiumchlorocephalum+TX, Cladosporium spp.+TX, Cladosporium tenuissimum+TX,Clonostachys rosea (EndoFine®)+TX, Colletotrichum acutatum+TX,Coniothyrium minitans (Cotans WG®)+TX, Coniothyrium spp.+TX,Cryptococcus albidus (YIELDPLUS®)+TX, Cryptococcus humicola+TX,Cryptococcus infirmo-miniatus+TX, Cryptococcus laurentii+TX,Cryptophlebia leucotreta granulovirus (Cryptex®)+TX, Cupriaviduscampinensis+TX, Cydia pomonella granulovirus (CYD-X®)+TX, Cydiapomonella granulovirus (Madex®+TX, Madex Plus®+TX, MadexMax/Carpovirusine®)+TX, Cylindrobasidium laeve (Stumpout®)+TX,Cylindrocladium+TX, Debaryomyces hansenii+TX, Drechslerahawaiinensis+TX, Enterobacter cloacae+TX, Enterobacteriaceae+TX,Entomophtora virulenta (Vektor®)+TX, Epicoccum nigrum+TX, Epicoccumpurpurascens+TX, Epicoccum spp.+TX, Filobasidium floriforme+TX, Fusariumacuminatum+TX, Fusarium chlamydosporum+TX, Fusarium oxysporum(Fusaclean®/Biofox C®)+TX, Fusarium proliferatum+TX, Fusarium spp.+TX,Galactomyces geotrichum+TX, Gliocladium catenulatum (Primastop®+TX,Prestop®)+TX, Gliocladium roseum+TX, Gliocladium spp. (SoilGard®)+TX,Gliocladium virens (Soilgard®)+TX, Granulovirus (Granupom®)+TX,Halobacillus halophilus+TX, Halobacillus litoralis+TX, Halobacillustrueperi+TX, Halomonas spp.+TX, Halomonas subglaciescola+TX, Halovibriovariabilis+TX, Hanseniaspora uvarum+TX, Helicoverpa armigeranucleopolyhedrovirus (Helicovex®)+TX, Helicoverpa zea nuclearpolyhedrosis virus (Gemstar®)+TX, Isoflavone—formononetin(Myconate®)+TX, Kloeckera apiculata+TX, Kloeckera spp.+TX, Lagenidiumgiganteum (Laginex®)+TX, Lecanicillium longisporum (Vertiblast®)+TX,Lecanicillium muscarium (Vertikil®)+TX, Lymantria Disparnucleopolyhedrosis virus (Disparvirus®)+TX, Marinococcus halophilus+TX,Meira geulakonigii+TX, Metarhizium anisopliae (Met52®)+TX, Metarhiziumanisopliae (Destruxin WP®)+TX, Metschnikowia fruticola (Shemer®)+TX,Metschnikowia pulcherrima+TX, Microdochium dimerum (Antibot®)+TX,Micromonospora coerulea+TX, Microsphaeropsis ochracea+TX, Muscodor albus620 (Muscudor®)+TX, Muscodor roseus strain A3-5+TX, Mycorrhizae spp.(AMykor®+TX, Root Maximizer®)+TX, Myrothecium verrucaria strainAARC-0255 (DiTera®)+TX, BROS PLUS®+TX, Ophiostoma piliferum strain D97(Sylvanex®)+TX, Paecilomyces farinosus+TX, Paecilomyces fumosoroseus(PFR-97®+TX, PreFeRal®)+TX, Paecilomyces linacinus (Biostat WP®)+TX,Paecilomyces lilacinus strain 251 (MeloCon WG®)+TX, Paenibacilluspolymyxa+TX, Pantoea agglomerans (BlightBan C9-1®)+TX, Pantoea spp.+TX,Pasteuria spp. (Econem®)+TX, Pasteuria nishizawae+TX, Penicilliumaurantiogriseum+TX, Penicillium billai (Jumpstart®+TX, TagTeam®)+TX,Penicillium brevicompactum+TX, Penicillium frequentans+TX, Penicilliumgriseofulvum+TX, Penicillium purpurogenum+TX, Penicillium spp.+TX,Penicillium viridicatum+TX, Phlebiopsis gigantean (Rotstop®)+TX,phosphate solubilizing bacteria (Phosphomeal®)+TX, Phytophthoracryptogea+TX, Phytophthora palmivora (Devine®)+TX, Pichia anomala+TX,Pichia guilermondii+TX, Pichia membranaefaciens+TX, Pichia onychis+TX,Pichia stipites+TX, Pseudomonas aeruginosa+TX, Pseudomonas aureofasciens(Spot-Less Biofungicide®)+TX, Pseudomonas cepacia+TX, Pseudomonaschlororaphis (AtEze®)+TX, Pseudomonas corrugate+TX, Pseudomonasfluorescens strain A506 (BlightBan A506®)+TX, Pseudomonas putida+TX,Pseudomonas reactans+TX, Pseudomonas spp.+TX, Pseudomonas syringae(Bio-Save®)+TX, Pseudomonas viridiflava+TX, Pseudomons fluorescens(Zequanox®)+TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®)+TX,Puccinia canaliculata+TX, Puccinia thlaspeos (Wood Warrior®)+TX, Pythiumparoecandrum+TX, Pythium oligandrum (Polygandron®+TX, Polyversum®)+TX,Pythium periplocum+TX, Rhanella aquatilis+TX, Rhanella spp.+TX, Rhizobia(Dormal®+TX, Vault®)+TX, Rhizoctonia+TX, Rhodococcus globerulus strainAQ719+TX, Rhodosporidium diobovatum+TX, Rhodosporidium toruloides+TX,Rhodotorula spp.+TX, Rhodotorula glutinis+TX, Rhodotorula graminis+TX,Rhodotorula mucilagnosa+TX, Rhodotorula rubra+TX, Saccharomycescerevisiae+TX, Salinococcus roseus+TX, Sclerotinia minor+TX, Sclerotiniaminor (SARRITOR®)+TX, Scytalidium spp.+TX, Scytalidium uredinicola+TX,Spodoptera exigua nuclear polyhedrosis virus (Spod-X®+TX, Spexit®)+TX,Serratia marcescens+TX, Serratia plymuthica+TX, Serratia spp.+TX,Sordaria fimicola+TX, Spodoptera littoralis nucleopolyhedrovirus(Littovir®)+TX, Sporobolomyces roseus+TX, Stenotrophomonasmaltophilia+TX, Streptomyces ahygroscopicus+TX, Streptomycesalbaduncus+TX, Streptomyces exfoliates+TX, Streptomyces galbus+TX,Streptomyces griseoplanus+TX, Streptomyces griseoviridis (Mycostop®)+TX,Streptomyces lydicus (Actinovate®)+TX, Streptomyces lydicus WYEC-108(ActinoGrow®)+TX, Streptomyces violaceus+TX, Tilletiopsis minor+TX,Tilletiopsis spp.+TX, Trichoderma asperellum (T34 Biocontrol®)+TX,Trichoderma gamsii (Tenet®)+TX, Trichoderma atroviride (Plantmate®)+TX,Trichoderma hamatum TH 382+TX, Trichoderma harzianum rifai(Mycostar®)+TX, Trichoderma harzianum T-22 (Trianum-P®+TX, PlantShieldHC®+TX, RootShield®+TX, Trianum-G®)+TX, Trichoderma harzianum T-39(Trichodex®)+TX, Trichoderma inhamatum+TX, Trichoderma koningii+TX,Trichoderma spp. LC 52 (Sentinel®)+TX, Trichoderma lignorum+TX,Trichoderma longibrachiatum+TX, Trichoderma polysporum (Binab T®)+TX,Trichoderma taxi+TX, Trichoderma virens+TX, Trichoderma virens (formerlyGliocladium virens GL-21) (SoilGuard®)+TX, Trichoderma viride+TX,Trichoderma viride strain ICC 080 (Remedier®)+TX, Trichosporonpullulans+TX, Trichosporon spp.+TX, Trichothecium spp.+TX, Trichotheciumroseum+TX, Typhula phacorrhiza strain 94670+TX, Typhula phacorrhizastrain 94671+TX, Ulocladium atrum+TX, Ulocladium oudemansii(Botry-Zen®)+TX, Ustilago maydis+TX, various bacteria and supplementarymicronutrients (Natural II®)+TX, various fungi (MillenniumMicrobes®)+TX, Verticillium chlamydosporium+TX, Verticillium lecanii(Mycotal®+TX, Vertalec®)+TX, Vip3Aa20 (VlPtera®)+TX, Virgibaclillusmarismortui+TX, Xanthomonas campestris pv. Poae (Camperico®)+TX,Xenorhabdus bovienii+TX, Xenorhabdus nematophilus; and

Plant extracts including: pine oil (Retenol®)+TX, azadirachtin (PlasmaNeem Oil®+TX, AzaGuard®+TX, MeemAzal®+TX, Molt-X®+TX, Botanical IGR(Neemazad®+TX, Neemix®)+TX, canola oil (Lilly Miller Vegol®)+TX,Chenopodium ambrosioides near ambrosioides (Requiem®)+TX, Chrysanthemumextract (Crisant®)+TX, extract of neem oil (Trilogy®)+TX, essentialsoils of Labiatae (Botania®)+TX, extracts of clove rosemary peppermintand thyme oil (Garden insect Killer®)+TX, Glycinebetaine(Greenstim®)+TX, garlic+TX, lemongrass oil (GreenMatch®)+TX, neemoil+TX, Nepeta cataria (Catnip oil)+TX, Nepeta catarina+TX, nicotine+TX,oregano oil (MossBuster®)+TX, Pedaliaceae oil (Nematon®)+TX,pyrethrum+TX, Quillaja saponaria (NemaQ®)+TX, Reynoutria sachalinensis(Regalia®+TX, Sakalia®)+TX, rotenone (Eco Roten®)+TX, Rutaceae plantextract (Soleo®)+TX, soybean oil (Ortho Ecosense®)+TX, tea tree oil(Timorex Gold®)+TX, thymus oil+TX, AGNIQUE® MMF+TX, BugOil®+TX, mixtureof rosemary sesame peppermint thyme and cinnamon extracts (EF 300®)+TX,mixture of clove rosemary and peppermint extract (EF 400®)+TX, mixtureof clove peppermint garlic oil and mint (Soil Shot®)+TX, kaolin(Screen®)+TX, storage glucam of brown algae (Laminarin®); and

pheromones including: blackheaded fireworm pheromone (3M SprayableBlackheaded Fireworm Pheromone®)+TX, Codling Moth Pheromone (Paramountdispenser-(CM)/Isomate C-Plus®)+TX, Grape Berry Moth Pheromone (3MMEC-GBM Sprayable Pheromone®)+TX, Leafroller pheromone (3M MEC-LRSprayable Pheromone®)+TX, Muscamone (Snip7 Fly Bait®+TX, Starbar PremiumFly Bait®)+TX, Oriental Fruit Moth Pheromone (3M oriental fruit mothsprayable Pheromone®)+TX, Peachtree Borer Pheromone (Isomate-P®)+TX,Tomato Pinworm Pheromone (3M Sprayable Pheromone®)+TX, Entostat powder(extract from palm tree) (Exosex CM®)+TX, (E+TX,Z+TX,Z)-3+TX,8+TX,11Tetradecatrienyl acetate+TX,(Z+TX,Z+TX,E)-7+TX,11+TX,13-Hexadecatrienal+TX,(E+TX,Z)-7+TX,9-Dodecadien-1-yl acetate+TX, 2-Methyl-1-butanol+TX,Calcium acetate+TX, Scenturion®+TX, Biolure®+TX, Check-Mate®+TX,Lavandulyl senecioate; and

Macrobials including: Aphelinus abdominalis+TX, Aphidius ervi(Aphelinus-System®)+TX, Acerophagus papaya+TX, Adalia bipunctata(Adalia-System®)+TX, Adalia bipunctata (Adaline®)+TX, Adalia bipunctata(Aphidalia®)+TX, Ageniaspis citricola+TX, Ageniaspis fuscicollis+TX,Amblyseius andersoni (Anderline®+TX, Andersoni-System®)+TX, Amblyseiuscalifomicus (Amblyline®+TX, Spical®)+TX, Amblyseius cucumeris(Thripex®+TX, Bugline Cucumeris®)+TX, Amblyseius fallacis(Fallacis®)+TX, Amblyseius swirskii (Bugline Swirskii®+TX,Swirskii-Mite®)+TX, Amblyseius womersleyi (WomerMite®)+TX, Amitushesperidum+TX, Anagrus atomus+TX, Anagyrus fusciventris+TX, Anagyruskamali+TX, Anagyrus loecki+TX, Anagyrus pseudococci (Citripar®)+TX,Anicetus benefices+TX, Anisopteromalus calandrae+TX, Anthocorisnemoralis (Anthocoris-System®)+TX, Aphelinus abdominalis (Apheline®+TX,Aphiline®)+TX, Aphelinus asychis+TX, Aphidius colemani (Aphipar®)+TX,Aphidius ervi (Ervipar®)+TX, Aphidius gifuensis+TX, Aphidius matricariae(Aphipar-M®)+TX, Aphidoletes aphidimyza (Aphidend®)+TX, Aphidoletesaphidimyza (Aphidoline®)+TX, Aphytis lingnanensis+TX, Aphytismelinus+TX, Aprostocetus hagenowii+TX, Atheta coriaria (Staphyline®)+TX,Bombus spp.+TX, Bombus terrestris (Natupol Beehive®)+TX, Bombusterrestris (Beeline®+TX, Tripol®)+TX, Cephalonomia stephanoderis+TX,Chilocorus nigritus+TX, Chrysoperla carnea (Chrysoline®)+TX, Chrysoperlacarnea (Chrysopa®)+TX, Chrysoperla rufilabris+TX, Cirrospilusingenuus+TX, Cirrospilus quadristriatus+TX, Citrostichusphyllocnistoides+TX, Closterocerus chamaeleon+TX, Closterocerus spp.+TX,Coccidoxenoides perminutus (Planopar®)+TX, Coccophagus cowperi+TX,Coccophagus lycimnia+TX, Cotesia flavipes+TX, Cotesia plutellae+TX,Cryptolaemus montrouzieri (Cryptobug®+TX, Cryptoline®)+TX, Cybocephalusnipponicus+TX, Dacnusa sibirica+TX, Dacnusa sibirica (Minusa®)+TX,Diglyphus isaea (Diminex®)+TX, Delphastus catalinae (Delphastus®)+TX,Delphastus pusillus+TX, Diachasmimorpha krausii+TX, Diachasmimorphalongicaudata+TX, Diaparsis jucunda+TX, Diaphorencyrtus aligarhensis+TX,Diglyphus isaea+TX, Diglyphus isaea (Miglyphus®+TX, Digline®)+TX,Dacnusa sibirica (DacDigline®+TX, Minex®)+TX, Diversinervus spp.+TX,Encarsia citrina+TX, Encarsia formosa (Encarsia Max®+TX, Encarline®+TX,En-Strip®)+TX, Eretmocerus eremicus (Enermix®)+TX, Encarsiaguadeloupae+TX, Encarsia haitiensis+TX, Episyrphus balteatus(Syrphidend®)+TX, Eretmoceris siphonini+TX, Eretmocerus californicus+TX,Eretmocerus eremicus (Ercal®+TX, Eretline E®)+TX, Eretmocerus eremicus(Bemimix®)+TX, Eretmocerus hayati+TX, Eretmocerus mundus (Bemipar®+TX,Eretline M®)+TX, Eretmocerus siphonini+TX, Exochomusquadripustulatus+TX, Feltiella acarisuga (Spidend®)+TX, Feltiellaacarisuga (Feltiline®)+TX, Fopius arisanus+TX, Fopius ceratitivorus+TX,Formononetin (Wirless Beehome®)+TX, Franklinothrips vespiformis(Vespop®)+TX, Galendromus occidentalis+TX, Goniozus legneri+TX,Habrobracon hebetor+TX, Harmonia axyridis (HarmoBeetle®)+TX,Heterorhabditis spp. (Lawn Patrol®)+TX, Heterorhabditis bacteriophora(NemaShield HB®+TX, Nemaseek®+TX, Terranem-Nam®+TX, Terranem®+TX,Larvanem®+TX, B-Green®+TX, NemAttack+TX, Nematop®)+TX, Heterorhabditismegidis (Nemasys+TX, BioNem+TX, Exhibitline Hm®+TX, Larvanem-M®)+TX,Hippodamia convergens+TX, Hypoaspis aculeifer (Aculeifer-System®+TX,Entomite-A®)+TX, Hypoaspis miles (Hypoline M®+TX, Entomite-M®)+TX,Lbalia leucospoides+TX, Lecanoideus floccissimus+TX, Lemophaguserrabundus+TX, Leptomastidea abnormis+TX, Leptomastix dactylopfi(Leptopar®)+TX, Leptomastix epona+TX, Lindorus lophanthae+TX, Lipolexisoregmae+TX, Lucilia caesar (Natufly®)+TX, Lysiphlebus testaceipes+TX,Macrolophus caliginosus (Mirical-N®+TX, Macroline+TX, Mirical®)+TX,Mesoseiulus longipes+TX, Metaphycus flavus+TX, Metaphycus lounsburyi+TX,Micromus angulatus (Milacewing®)+TX, Microterys flavus+TX, Muscidifuraxraptorellus and Spalangia cameroni (Biopar®)+TX, Neodryinustyphlocybae+TX, Neoseiulus califomicus+TX, Neoseiulus cucumeris(THRYPEX®)+TX, Neoseiulus fallacis+TX, Nesideocoris tenuis(NesidioBug®+TX, Nesibug®)+TX, Ophyra aenescens (Biofly®)+TX, Oriusinsidiosus (Thripor-I®+TX, Oriline I®)+TX, Orius laevigatus(Thripor-L®+TX, Oriline I®)+TX, Orius majusculus (Oriline M®)+TX, Oriusstrigicollis (Thripor-S®)+TX, Pauesia juniperorum+TX, Pediobiusfoveolatus+TX, Phasmarhabditis hermaphrodita (Nemaslug®)+TX,Phymastichus coffea+TX, Phytoseiulus macropilus+TX, Phytoseiuluspersimilis (Spidex®+TX, Phytoline P®)+TX, Podisus maculiventris(Podisus®)+TX, Pseudacteon curvatus+TX, Pseudacteon obtusus+TX,Pseudacteon tricuspis+TX, Pseudaphycus maculipennis+TX, Pseudleptomastixmexicana+TX, Psyllaephagus pilosus+TX, Psyttalia concolor (complex)+TX,Quadrastichus spp.+TX, Rhyzobius lophanthae+TX, Rodolia cardinalis+TX,Rumina decollate+TX, Semielacher petiolatus+TX, Sitobion avenae(Ervibank®)+TX, Steinernema carpocapsae (Nematac C®+TX, Millenium®+TX,BioNem C®+TX, NemAttack®+TX, Nemastar®+TX, Capsanem®)+TX, Steinernemafeltiae (NemaShield®+TX, Nemasys F®+TX, BioNem F®+TX,Steinernema-System®+TX, NemAttack®+TX, Nemaplus®+TX, Exhibitline Sf®+TX,Scia-Rid®+TX, Entonem®)+TX, Steinernema kraussei (Nemasys L®+TX, BioNemL®+TX, Exhibitline Srb®)+TX, Steinernema riobrave (BioVector®+TX,BioVektor®)+TX, Steinernema scapterisci (Nematac S®)+TX, Steinernemaspp.+TX, Steinernematid spp. (Guardian Nematodes®)+TX, Stethoruspunctillum (Stethorus®)+TX, Tamarixia radiate+TX, Tetrastichussetifer+TX, Thripobius semiluteus+TX, Torymus sinensis+TX, Trichogrammabrassicae (Tricholine B®)+TX, Trichogramma brassicae (Tricho-Strip®)+TX,Trichogramma evanescens+TX, Trichogramma minutum+TX, Trichogrammaostriniae+TX, Trichogramma platneri+TX, Trichogramma pretiosum+TX,Xanthopimpla stemmator; and

other biologicals including: abscisic acid+TX, bioSea®+TX,Chondrostereum purpureum (Chontrol Paste®)+TX, Colletotrichumgloeosporioides (Callego®)+TX, Copper Octanoate (Cueva®)+TX, Delta traps(Trapline D®)+TX, Erwinia amylovora (Harpin) (ProAct®+TX, Ni-HIBIT GoldCST®)+TX, Ferri-phosphate (Ferramol®)+TX, Funnel traps (Trapline Y®)+TX,Gallex®+TX, Growers Secret®+TX, Homo-brassonolide+TX, Iron Phosphate(Lilly Miller Worry Free Ferramol Slug & Snail Bait®)+TX, MCP hail trap(Trapline F®)+TX, Microctonus hyperodae+TX, Mycoleptodiscus terrestris(Des-X®)+TX, BioGain®+TX, Aminomite®+TX, Zenox®+TX, Pheromone trap(Thripline Ams®)+TX, potassium bicarbonate (MilStop®)+TX, potassiumsalts of fatty acids (Sanova®)+TX, potassium silicate solution(SD-Matrix®)+TX, potassium iodide+potassiumthiocyanate (Enzicur®)+TX,SuffOil-X®+TX, Spider venom+TX, Nosema locustae (Semaspore OrganicGrasshopper Control®)+TX, Sticky traps (Trapline YF®+TX, RebellAmarillo®)+TX and Traps (Takitrapline y+B®)+TX.

The references in brackets behind the active ingredients, e.g.[3878-19-1] refer to the Chemical Abstracts Registry number. The abovedescribed mixing partners are known. Where the active ingredients areincluded in “The Pesticide Manual” [The Pesticide Manual—A WorldCompendium; Thirteenth Edition; Editor: C. D. S. TomLin; The BritishCrop Protection Council], they are described therein under the entrynumber given in round brackets hereinabove for the particular compound;for example, the compound “abamectin” is described under entry number(1). Where “[CCN]” is added hereinabove to the particular compound, thecompound in question is included in the “Compendium of Pesticide CommonNames”, which is accessible on the internet [A. Wood; Compendium ofPesticide Common Names, Copyright 1995-2004]; for example, the compound“acetoprole” is described under the internet addresshttp://www.alanwood.net/pesticides/acetoprole.html.

Most of the active ingredients described above are referred tohereinabove by a so-called “common name”, the relevant “ISO common name”or another “common name” being used in individual cases. If thedesignation is not a “common name”, the nature of the designation usedinstead is given in round brackets for the particular compound; in thatcase, the IUPAC name, the IUPAC/Chemical Abstracts name, a “chemicalname”, a “traditional name”, a “compound name” or a “development code”is used or, if neither one of those designations nor a “common name” isused, an “alternative name” is employed. “CAS Reg. No” means theChemical Abstracts Registry Number.

The active ingredient mixture of the compounds of formula I selectedfrom Tables 1 to 12 and Table P with active ingredients described abovecomprises a compound selected from Tables 1 to 12 and Table P and anactive ingredient as described above preferably in a mixing ratio offrom 100:1 to 1:6000, especially from 50:1 to 1:50, more especially in aratio of from 20:1 to 1:20, even more especially from 10:1 to 1:10, veryespecially from 5:1 and 1:5, special preference being given to a ratioof from 2:1 to 1:2, and a ratio of from 4:1 to 2:1 being likewisepreferred, above all in a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4,or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5,or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75,or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750,or 2:750, or 4:750. Those mixing ratios are by weight.

The mixtures as described above can be used in a method for controllingpests, which comprises applying a composition comprising a mixture asdescribed above to the pests or their environment, with the exception ofa method for treatment of the human or animal body by surgery or therapyand diagnostic methods practised on the human or animal body.

The mixtures comprising a compound of formula I selected from Tables 1to 12 and Table P and one or more active ingredients as described abovecan be applied, for example, in a single “ready-mix” form, in a combinedspray mixture composed from separate formulations of the single activeingredient components, such as a “tank-mix”, and in a combined use ofthe single active ingredients when applied in a sequential manner, i.e.one after the other with a reasonably short period, such as a few hoursor days. The order of applying the compounds of formula I selected fromTables 1 to 12 and Table P and the active ingredients as described aboveis not essential for working the present invention.

The compositions according to the invention can also comprise furthersolid or liquid auxiliaries, such as stabilizers, for exampleunepoxidized or epoxidized vegetable oils (for example epoxidizedcoconut oil, rapeseed oil or soya oil), antifoams, for example siliconeoil, preservatives, viscosity regulators, binders and/or tackifiers,fertilizers or other active ingredients for achieving specific effects,for example bactericides, fungicides, nematocides, plant activators,molluscicides or herbicides.

The compositions according to the invention are prepared in a mannerknown per se, in the absence of auxiliaries for example by grinding,screening and/or compressing a solid active ingredient and in thepresence of at least one auxiliary for example by intimately mixingand/or grinding the active ingredient with the auxiliary (auxiliaries).These processes for the preparation of the compositions and the use ofthe compounds I for the preparation of these compositions are also asubject of the invention.

The application methods for the compositions, that is the methods ofcontrolling pests of the abovementioned type, such as spraying,atomizing, dusting, brushing on, dressing, scattering or pouring—whichare to be selected to suit the intended aims of the prevailingcircumstances—and the use of the compositions for controlling pests ofthe abovementioned type are other subjects of the invention. Typicalrates of concentration are between 0.1 and 1000 ppm, preferably between0.1 and 500 ppm, of active ingredient. The rate of application perhectare is generally 1 to 2000 g of active ingredient per hectare, inparticular 10 to 1000 g/ha, preferably 10 to 600 g/ha.

A preferred method of application in the field of crop protection isapplication to the foliage of the plants (foliar application), it beingpossible to select frequency and rate of application to match the dangerof infestation with the pest in question. Alternatively, the activeingredient can reach the plants via the root system (systemic action),by drenching the locus of the plants with a liquid composition or byincorporating the active ingredient in solid form into the locus of theplants, for example into the soil, for example in the form of granules(soil application). In the case of paddy rice crops, such granules canbe metered into the flooded paddy-field.

The compounds of the invention and compositions thereof are also besuitable for the protection of plant propagation material, for exampleseeds, such as fruit, tubers or kernels, or nursery plants, againstpests of the abovementioned type. The propagation material can betreated with the compound prior to planting, for example seed can betreated prior to sowing. Alternatively, the compound can be applied toseed kernels (coating), either by soaking the kernels in a liquidcomposition or by applying a layer of a solid composition. It is alsopossible to apply the compositions when the propagation material isplanted to the site of application, for example into the seed furrowduring drilling. These treatment methods for plant propagation materialand the plant propagation material thus treated are further subjects ofthe invention. Typical treatment rates would depend on the plant andpest/fungi to be controlled and are generally between 1 to 200 grams per100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds,such as between 10 to 100 grams per 100 kg of seeds.

The term seed embraces seeds and plant propagules of all kinds includingbut not limited to true seeds, seed pieces, suckers, corns, bulbs,fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like andmeans in a preferred embodiment true seeds.

The present invention also comprises seeds coated or treated with orcontaining a compound of formula I. The term “coated or treated withand/or containing” generally signifies that the active ingredient is forthe most part on the surface of the seed at the time of application,although a greater or lesser part of the ingredient may penetrate intothe seed material, depending on the method of application. When the saidseed product is (re)planted, it may absorb the active ingredient. In anembodiment, the present invention makes available a plant propagationmaterial adhered thereto with a compound of formula (I). Further, it ishereby made available, a composition comprising a plant propagationmaterial treated with a compound of formula (I).

Seed treatment comprises all suitable seed treatment techniques known inthe art, such as seed dressing, seed coating, seed dusting, seed soakingand seed pelleting. The seed treatment application of the compoundformula (I) can be carried out by any known methods, such as spraying orby dusting the seeds before sowing or during the sowing/planting of theseeds.

BIOLOGICAL EXAMPLES Example B1: Activity Against Spodoptera littoralis(Egyptian Cotton Leaf Worm)

Cotton leaf discs were placed on agar in 24-well microtiter plates andsprayed with aqueous test solutions prepared from 10,000 ppm DMSO stocksolutions. After drying the leaf discs were infested with five L1larvae. The samples were assessed for mortality, anti-feedant effect,and growth inhibition in comparison to untreated samples 3 days afterinfestation. Control of Spodoptera littoralis by a test sample is whenat least one of mortality, anti-feedant effect, and growth inhibition ishigher than the untreated sample.

The following compounds resulted in at least 80% control at anapplication rate of 200 ppm: P1, P2, P4, P6, P7, P9, P11, P13, P14, P16,P17, P18, P19, P20, P21, P22, P23, P24, P25, P26, P27, P28, P29, P32,P35, P37, P38, P39, P41, P42, P40, P44, P45, P48, P50, P52 and P53.

Example B2: Activity Against Spodoptera littoralis (Egyptian Cotton LeafWorm)

Test compounds were applied by pipette from 10,000 ppm DMSO stocksolutions into 24-well plates and mixed with agar. Lettuce seeds wereplaced on the agar and the multi well plate was closed by another platewhich contains also agar. After 7 days the roots have absorbed thecompound and the lettuce has grown into the lid plate. The lettuce leafswere now cut off into the lid plate. Spodoptera eggs were pipettedthrough a plastic stencil on a humid gel blotting paper and the plateclosed with it. The samples were assessed for mortality, anti-feedanteffect and growth inhibition in comparison to untreated samples 6 daysafter infestation.

The following compounds gave an effect of at least 80% in at least oneof the three categories (mortality, anti-feedancy, or growth inhibition)at a test rate of 12.5 ppm: P6, P7, P9, P14, P16, P17, P20, P21, P22,P23, P25, P26, P27, P28, P29, P39, P41, P40, P48, P50 and P52.

Example B3: Activity Against Plutella xylostella (Diamond Back Moth)

24-well microtiter plates with artificial diet were treated with aqueoustest solutions prepared from 10,000 ppm DMSO stock solutions bypipetting. After drying, the plates were infested with L2 larvae (10 to15 per well). The samples were assessed for mortality and growthinhibition in comparison to untreated samples 5 days after infestation.

The following compounds gave an effect of at least 80% in at least oneof the two categories (mortality or growth inhibition) at an applicationrate of 200 ppm: P6, P7, P8, P9, P11, P13, P14, P16, P17, P20, P21, P22,P23, P24, P25, P26, P27, P28, P29, P32, P35, P37, P38, P39, P41, P40,P45, P48, P50, P52, P53 and P54.

Example B4: Activity Against Diabrotica Balteata (Corn Root Worm)

Maize sprouts, placed on an agar layer in 24-well microtiter plates weretreated with aqueous test solutions prepared from 10,000 ppm DMSO stocksolutions by spraying. After drying, the plates were infested with L2larvae (6 to 10 per well). The samples were assessed for mortality andgrowth inhibition in comparison to untreated samples 4 days afterinfestation.

The following compounds gave an effect of at least 80% in at least oneof the two categories (mortality or growth inhibition) at an applicationrate of 200 ppm: P1, P2, P5, P6, P7, P8, P9, P11, P13, P14, P16, P17,P18, P19, P20, P21, P22, P23, P24, P25, P26, P27, P28, P29, P32, P34,P35, P36, P37, P38, P39, P41, P40, P45, P46, P47, P48, P50, P52, P53 andP54.

Example B5: Activity Against Myzus persicae (Green Peach Aphid)

Sunflower leaf discs were placed on agar in a 24-well microtiter plateand sprayed with aqueous test solutions prepared from 10,000 ppm DMSOstock solutions. After drying, the leaf discs were infested with anaphid population of mixed ages. The samples were assessed for mortality6 days after infestation.

The following compounds resulted in at least 80% mortality at anapplication rate of 200 ppm: P4, P6, P7, P9, P11, P12, P13, P14, P16,P17, P20, P21, P22, P23, P26, P27, P28, P29, P34, P37, P39, P41, P40,P43, P45, P46, P47, P48, P50, P52 and P54.

Example B6: Activity Against Myzus persicae (Green Peach Aphid)

Roots of pea seedlings infested with an aphid population of mixed ageswere placed directly in the aqueous test solutions prepared from 10,000DMSO stock solutions. The samples were assessed for mortality 6 daysafter placing seedlings in test solutions.

The following compounds resulted in at least 80% mortality at a testrate of 24 ppm: P9, P12, P14, P15, P17, P23, P27, P29, P36, P37, P39,P41, P40, P43, P44, P45, P46, P47 and P54.

Example B7: Activity Against Frankliniella occidentalis (Western FlowerThrips)

Sunflower leaf discs were placed on agar in 24-well microtiter platesand sprayed with aqueous test solutions prepared from 10,000 DMSO stocksolutions. After drying the leaf discs were infested with aFrankliniella population of mixed ages. The samples were assessed formortality 7 days after infestation.

The following compounds resulted in at least 80% mortality at anapplication rate of 200 ppm: P3, P6, P7, P8, P9, P13, P14, P17, P21,P22, P23, P26, P27, P28, P41, P40, P45, P46, P48, P50, P52 and P54.

Example B8: Activity Against Bemisia tabaci (Cotton White Fly)

Cotton leaf discs were placed on agar in 24-well microtiter plates andsprayed with aqueous test solutions prepared from 10,000 ppm DMSO stocksolutions. After drying the leaf discs were infested with adult whiteflies. The samples were checked for mortality 6 days after incubation.

The following compounds resulted in at least 80% mortality at anapplication rate of 200 ppm: P6, P14, P17, P27 P32, P37, P40, P45 andP48.

Example B9: Activity Against Euschistus heros(Neotropical Brown StinkBug)

Soybean leaf on agar in 24-well microtiter plates were sprayed withaqueous test solutions prepared from 10,000 ppm DMSO stock solutions.After drying the leaf were infested with N-2 nymphs. The samples wereassessed for mortality and growth inhibition in comparison to untreatedsamples 5 days after infestation.

The following compounds gave an effect of at least 80% in at least oneof the two categories (mortality or growth inhibition) at an applicationrate of 200 ppm: P3, P4, P6, P7, P9, P11, P14, P17, P20, P21, P22, P23,P24, P25, P26, P27, P28, P37, P39, P41, P40, P45, P47, P48, P50, P52 andP54.

Example B10: Activity Against Tetranychus urticae (Two-Spotted SpiderMite)

Bean leaf discs on agar in 24-well microtiter plates were sprayed withaqueous test solutions prepared from 10,000 ppm DMSO stock solutions.After drying the leaf discs were infested with a mite population ofmixed ages. The samples were assessed for mortality on mixed population(mobile stages) 8 days after infestation.

The following compound resulted in at least 80% mortality at anapplication rate of 200 ppm: P19.

Example B11: Activity Against Aedes aegypti (Yellow Fever Mosquito)

Test solutions, at an application rate of 200 ppm in ethanol, wereapplied to 12-well tissue culture plates. Once the deposits were dry,five, two to five days old adult female Aedes aegypti were added to eachwell, and sustained with a 10% sucrose solution in a cotton wool plug.Assessment of knockdown was made one hour after introduction, andmortality was assessed at 24 and 48 hours after introduction.

The following compounds gave at least 80% control of Aedes aegypti after48 h and/or 24 h: P7, P17, P22, P26, P27, P39 and P40.

Example B12: Activity Against Thrips tabaci (Onion Thrips)

Sunflower leaf discs were placed on agar in 24-well microtiter platesand sprayed with aqueous test solutions prepared from 10,000 ppm DMSOstock solutions. After drying the leaf discs were infested with a thripspopulation of mixed ages. The samples were assessed for mortality 6 daysafter infestation.

The following compounds resulted in at least 80% mortality at anapplication rate of 200 ppm: P6, P7, P13, P14, P15, P17, P22, P23, P25,P26, P27, P29, P32, P41, P42, P40 and P45.

Example B13: Activity Against Anopheles stephensi (Indian MalariaMosquito)

Test solutions, at an application rate of 200 ppm in ethanol, wereapplied to 12-well tissue culture plates. Once the deposits were dry,five, two to five day old adult female Anopheles stephensi were added toeach well, and sustained with a 10% sucrose solution in a cotton woolplug. Assessment of knockdown was made one hour after introduction, andmortality was assessed at 24 and 48 hours after introduction.

The following compounds gave at least 80% control of Anopheles stephensiafter 48 h and/or 24 h: P17, P22, P26, P27 and P39.

1. A compound of formula I

wherein G₁ is nitrogen or CR₂; G₂ is nitrogen or CR₃; G₃ is nitrogen orCR₄; G₄ is nitrogen or CR₅; G₅ is nitrogen or CR₆, with the proviso thatnot more than 2 nitrogens as G may follow consecutively; R₂, R₃, R₄, R₅or R₆ are, independently from each other, hydrogen, halogen,C₁-C₄haloalkyl, C₁-C₄haloalkyl substituted by one or two hydroxy,C₁-C₄haloalkyl substituted by one or two methoxy, C₁-C₄haloalkylsubstituted by one or two cyano; or R₂, R₃, R₄, R₅ or R₆ are,independently from each other, C₁-C₄haloalkylsulfanyl,C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl, C₁-C₄haloalkoxy, SF₅,phenylcarbonylthio, cyano, mercapto, C₁-C₄alkoxycarbonyl,C₁-C₄alkylcarbonyl or —C(O)C₁-C₄haloalkyl; or R₂, R₃, R₄, R₅ or R₆ are,independently from each other, C₃-C₆cycloalkyl which can be mono- orpolysubstituted by substituents selected from the group consisting ofhalogen, cyano and C₁-C₄alkyl; or two adjacent R_(i), wherein R_(i) isselected from R₂, R₃, R₄, R₅ and R₆, taken together may form a fragment—OCH₂O— or —OCF₂O—, R₈ is hydrogen, C₁-C₄alkyl or C₁-C₄haloalkyl; R₇ isa radical selected from the group consisting of formula Q₁ and Q₂

wherein the arrow denotes the point of attachment to the triazole ring;and wherein A represents CH or N; Q is phenyl which can be mono- orpolysubstituted by substituents selected from the group consisting ofhalogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl; or Q is a five- toten-membered monocyclic or fused bicyclic ring system linked via acarbon atom to the ring which contains the group A, said ring system canbe aromatic, partially saturated or fully saturated and contains 1 to 4hetero atoms selected from the group consisting of nitrogen, oxygen andsulfur, it not being possible for each ring system to contain more than2 oxygen atoms and more than 2 sulfur atoms, said five- to ten-memberedring system can be mono- to polysubstituted by substituentsindependently selected from the group consisting of halogen, cyano,C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy,C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl; or Q is a five- tosix-membered, aromatic, partially saturated or fully saturated ringsystem linked via a nitrogen atom to the ring which contains the groupA, said ring system can be mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano, C₁-C₄alkyl,C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy, C₁-C₄alkylsulfanyl,C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, —C(O)C₁-C₄alkyl,C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyland —C(O)C₁-C₄haloalkyl; and said ring system contains 1, 2 or 3heteroatoms selected from the group consisting of nitrogen, oxygen andsulfur, where said ring system may not contain more than one oxygen atomand not more than one sulfur atom; or Q is C₃-C₆cycloalkyl, orC₃-C₆cycloalkyl mono- or polysubstituted by substituents selected fromthe group consisting of halogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl,C₃-C₆cycloalkyl and phenyl, wherein said phenyl can be mono- orpolysubstituted by substituents selected from the group consisting ofhalogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl; or Q is C₂-C₆alkenyl, orC₂-C₆alkenyl mono- or polysubstituted by substituents selected from thegroup consisting of halogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl,C₁-C₄alkoxy, C₃-C₆cycloalkyl and phenyl, wherein said phenyl can bemono- or polysubstituted by substituents selected from the groupconsisting of halogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl,C₁-C₄haloalkoxy, C₁-C₄alkoxy, C₁-C₄haloalkylsulfanyl,C₁-C₄halo-alkylsulfinyl, C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl;or Q is C₂-C₆alkynyl, or C₂-C₆alkynyl mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano,C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl, tri(C₁-C₄alkyl)silyl andphenyl, wherein said phenyl can be mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano,C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy,C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyland —C(O)C₁-C₄haloalkyl; or Q is C₁-C₆haloalkylsulfanyl,C₁-C₆haloalkylsulfinyl, C₁-C₆haloalkylsulfonyl, C₁-C₆haloalkoxy,—C(O)C₁-C₄haloalkyl, C₁-C₆alkylsulfanyl, C₁-C₆alkylsulfinyl, orC₁-C₆alkylsulfonyl; X is S, SO or SO₂; and R₁ is C₁-C₄alkyl,C₁-C₄haloalkyl, C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl; or R₁ isC₃-C₆cycloalkyl mono- or polysubstituted by substituents selected fromthe group consisting of halogen, cyano and C₁-C₄alkyl; or R₁ isC₃-C₆cycloalkyl-C₁-C₄alkyl mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano and C₁-C₄alkyl; orR₁ is C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; and agrochemicallyacceptable salts, stereoisomers, enantiomers, tautomers and N-oxides ofthe compounds of formula I.
 2. A compound of formula I according toclaim 1, wherein Q is selected from the group consisting of thefollowing heterocyclic groups: pyrrolyl; pyrazolyl; isoxazolyl; furanyl;thienyl; imidazolyl; oxazolyl; thiazolyl; isothiazolyl; triazolyl;oxadiazolyl; thiadiazolyl; tetrazolyl; furyl; pyridyl; pyrimidyl;pyrazinyl; pyridazinyl; triazinyl, pyranyl; quinazolinyl; isoquinolinyl;indolizinyl; isobenzofuranylnaphthyridinyl; quinoxalinyl; cinnolinyl;phthalazinyl; benzothiazolyl; benzoxazolyl; benzotriazolyl; indazolyl;indolyl; (1H-pyrrol-1-yl)-; (1H-pyrrol-2-yl)-; (1H-pyrrol-3-yl)-;(1H-pyrazol-1-yl)-; (1H-pyrazol-3-yl)-; (3H-pyrazol-3-yl)-;(1H-pyrazol-4-yl)-; (3-isoxazolyl)-; (5-isoxazolyl)-; (2-furanyl)-;(3-furanyl)-; (2-thienyl)-; (3-thienyl)-; (1H-imidazol-2-yl)-;(1H-imidazol-4-yl)-; (1H-imidazol-5-yl)-; (2-oxazol-2-yl)-;(oxazol-4-yl)-; (oxazol-5-yl)-; (thiazol-2-yl)-; (thiazol-4-yl)-;(thiazol-5-yl)-; (isothiazol-3-yl)-; (isothiazol-5-yl)-;(1H-1,2,3-triazol-1-yl)-; (1H-1,2,4-triazol-3-yl)-;(4H-1,2,4-triazol-4-yl)-; (1H-1,2,4-triazol-1-yl)-;(1,2,3-oxadiazol-2-yl)-; (1,2,4-oxadiazol-3-yl)-;(1,2,4-oxadiazol-4-yl)-; (1,2,4-oxadiazol-5-yl)-;(1,2,3-thiadiazol-2-yl)-; (1,2,4-thiadiazol-3-yl)-;(1,2,4-thiadiazol-4-yl)-; (1,3,4-thiadiazol-5-yl)-; (1H-tetrazol-1-yl)-;(1H-tetrazol-5-yl)-; (2H-tetrazol-5-yl)-; (2-pyridyl)-; (3-pyridyl)-;(4-pyridyl)-; (2-pyrimidinyl)-; (4-pyrimidinyl)-; (5-pyrimidinyl)-;(2-pyrazinyl)-; (3-pyridazinyl)-; (4-pyridazinyl)-;(1,3,5-triazin-2-yl)-; (1,2,4-triazin-5-yl)-; (1,2,4-triazin-6-yl)-;(1,2,4-triazin-3-yl)-; (furazan-3-yl)-; (2-quinolinyl)-;(3-quinolinyl)-; (4-quinolinyl)-; (5-quinolinyl)-; (6-quinolinyl)-;(3-isoquinolnyl)-; (4-isoquinolnyl)-; (2-quinozolinyl)-;(2-quinoxalinyl)-; (5-quinoxalinyl)-; (pyrido[2,3-b]pyrazin-7-yl)-;(benzoxazol-5-yl)-; (benzothiazol-5-yl)-; (benzo[b]thien-2-yl) and(benzo[1,2,5]oxadiazol-5-yl)-; indolinyl and tetrahydroquinolynyl.
 3. Acompound of formula I according to claim 1, wherein Q is selected fromthe group consisting of J-0 to J-51:

wherein each group J-0 to J-48 is mono-, di- or trisubstituted with Rx,wherein each Rx is, independently selected from hydrogen, halogen,cyano, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy,C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl.
 4. A compound of formulaI according to claim 1, represented by the compounds of formula I-1

wherein A, Q, G₁, G₂, G₃, G₄, and G₅ are as defined under formula I inclaim 1; X₁ is S, SO or SO₂; R₁₁ is methyl, ethyl, n-propyl, i-propyl orcyclopropylmethyl; and R₈ is as defined under formula I in claim
 1. 5. Acompound of formula I according to claim 1 represented by the compoundsof formula I-2

wherein A, G₁, G₂, G₃, G₄, and G₅ are as defined under formula I inclaim 1; X₂ is S, SO or SO₂; R₁₂ is methyl, ethyl, n-propyl, i-propyl orcyclopropylmethyl; R₈ is as defined above under formula I in claim 1;and Qa₁ is selected from the group consisting of

wherein each group J-0 to J-48 is mono-, di- or trisubstituted with Rx,wherein each Rx is, independently selected from hydrogen, halogen,cyano, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy,C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl.
 6. A compound of formulaI according to claim 1, represented by the compounds of formula I-3

wherein A is N or CH; R₁₀ is pyridyl or pyrimidyl mono- orpolysubstituted by C₁-C₄haloalkyl; X₃ is S or SO₂; Qa₂ is selected fromthe group consisting of

wherein each group J-0 to J-48 is mono-, di- or trisubstituted with Rx,wherein each Rx is, independently selected from hydrogen, halogen,cyano, C₁-C₄haloalkyl and C₁-C₄alkoxy; R₁₃ is C₁-C₄alkyl; and R₈ isC₁-C₄alkyl.
 7. A compound of formula I according to claim 1, representedby the compounds of formula I-4

wherein R₁₀′ is pyridyl or pyrimidyl monosubstituted by C₁-C₄haloalkyl;and Qa₄ is selected from the group consisting of

wherein each Rx is independently selected from hydrogen, halogen, cyano,C₁-C₄haloalkyl and C₁-C₄alkoxy.
 8. A compound of formula I according toclaim 1, represented by the compounds of formula I-5

wherein R₅ is C₁-C₄haloalkyl; and Qa₅ is selected from the groupconsisting of

wherein each Rx is, independently selected from hydrogen, halogen,cyano, C₁-C₄haloalkyl and C₁-C₄alkoxy.
 9. A compound of formula Iaccording to claim 1, represented by the compounds of formula I-6

wherein R₆ is C₁-C₄haloalkyl; and Qa₆ is selected from the groupconsisting of

wherein each Rx is, independently selected from hydrogen, halogen andcyano.
 10. A compound of formula I according to claim 1, represented bythe compounds of formula I-1p

wherein A, Q, G₁, G₂, G₃, G₄, and G₅ are as defined under formula I inclaim 1; X₁ is S, SO or SO₂; R₁₁ is methyl, ethyl, n-propyl, i-propyl orcyclopropylmethyl; and R₈ is as defined under formula I in claim
 1. 11.A compound of formula I according to claim 1 represented by thecompounds of formula I-2p

wherein A, Q, G₁, G₂, G₃, G₄, and G₅ are as defined under formula I inclaim 1; X₂ is S, SO or SO₂; R₁₂ is methyl, ethyl, n-propyl, i-propyl orcyclopropylmethyl; R₈ is as defined above under formula I in claim 1;and Q is selected from the group consisting of

wherein each group J-0 to J-43 is mono-, di- or trisubstituted with Rx,wherein each Rx is, independently selected from hydrogen, halogen,cyano, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy,C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl.
 12. A pesticidalcomposition, which comprises at least one compound of formula Iaccording to claim 1 or, where appropriate, a tautomer thereof, in eachcase in free form or in agrochemically utilizable salt form, as activeingredient and at least one auxiliary.
 13. A method for controllingpests, which comprises applying a composition according to claim 12 tothe pests or their environment with the exception of a method fortreatment of the human or animal body by surgery or therapy anddiagnostic methods practised on the human or animal body.
 14. A methodfor the protection of plant propagation material from the attack bypests, which comprises treating the propagation material or the site,where the propagation material is planted, with a composition accordingto claim
 12. 15. A compound of formula (Iab)

wherein R₁, R₈, G₁, G₂, G₃, G₄, G₅, X and A are as defined under formulaI in claim
 1. 16. A compounds of formula XVII-Int

wherein R₁, R₈, G₁, G₂, G₃, G₄, G₅, X and A are as defined under formulaI in claim 1, and Yb₃ is —B(OH)₂, —B(OR_(b2))₂, in which R_(b2) is aC₁-C₆alkyl or Yb₃ is

(a 4,4,5,5-tetramethyl-1,3,2-dioxaborolane group).